JP7631040B2 - Fire-resistant resin composition - Google Patents

Description

The present invention relates to a fire-resistant resin composition, and more specifically, to a fire-resistant resin composition that has expandability and can block a partition penetration.

In buildings such as apartment buildings, office buildings, and schools, partitions such as walls are often provided with compartment penetrations to allow for the passage of long objects such as cables and pipes. Compartment penetrations are required to have a fire-resistant structure to prevent the spread of fire to other compartments in the event of a fire in one compartment. Partitions are generally hollow walls made of two walls with a hollow space between them.

One known method for making a compartment penetration fireproof is, for example, filling the gap between the long insert and the penetration hole with an amorphous filler such as fireproof putty. When using an amorphous filler, a tubular member made of fireproof material may also be placed between the inside of the penetration hole in each wall section and the insert (see, for example, Patent Documents 1 and 2).

Patent No. 6150933 Patent No. 6348320

However, when amorphous fillers are used to treat fireproofing of compartment penetrations, there is variation between workers, and sufficient fire resistance may not be achieved. Furthermore, when installing fireproofing materials and their accessories within the structure, it may not be clear to what extent they have been installed (quantity, thickness, length, etc.), or it may be impossible to determine whether they have been installed according to regulations. Therefore, in order to check whether fireproofing materials have been installed according to regulations, it is necessary to destroy the compartment penetration treatment structure and check the internal structure.

In addition, in a compartment penetration structure in which long inserts such as cables and piping are inserted inside, if the insert is moved after the compartment penetration structure is applied, the fireproof material installed inside may shift from its appropriate position. External forces such as earthquakes may also cause the fireproof material to shift from its appropriate position. Furthermore, if the fireproof material does not expand uniformly but expands unevenly, it may shift from its appropriate position or fall off. In this way, it becomes difficult to achieve the fire resistance performance desired for the fireproof structure of the compartment penetration part.

In light of the above issues, a method has been considered in which a thermal expansion sheet with a high expansion ratio is installed in the compartment penetration part without using an amorphous filler in the structure. The thermal expansion sheet can be obtained, for example, by filling it with a high amount of thermal expansion material, and can increase the expansion ratio. In the event of a fire, it will expand sufficiently due to the flames, blocking the compartment penetration part and suppressing the spread of the fire.
However, when the thermal expansion material is highly filled, the residue of the sheet tends to become brittle and may be blown away by a flame, etc. Therefore, there are cases where the compartment penetration part cannot be sufficiently blocked and the spread of fire cannot be suppressed.

Therefore, the objective of the present invention is to provide a fire-resistant resin composition that can properly block the compartment penetration part in the event of a fire, suppress the spread of the fire, and harden the expansion residue to maintain the blockage of the compartment penetration part.

The present invention has been made to solve the above problems, and the gist of the present invention is as follows.
[1] A fire-resistant resin composition for use in a fire-resistant structure of a building, comprising a resin, a plasticizer, an additive, and a thermally expandable layered inorganic material, wherein the resin comprises at least one selected from the group consisting of polyvinyl acetal, polybutene, and a rubber component, and the additive is at least one selected from the group consisting of a flame retardant, a heat-absorbing agent, a lubricant, and an inorganic filler.
[2] The fire-resistant resin composition according to [1], wherein the rubber component is at least one selected from the group consisting of chloroprene rubber, natural rubber, butyl rubber, styrene-butadiene rubber, nitrile-butadiene rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, and acrylic rubber.
[3] The fire-resistant resin composition according to [1] or [2], wherein the resin further contains at least one selected from the group consisting of polyphenylene oxide and petroleum resin.
[4] The fire-resistant resin composition according to any one of [1] to [3], wherein the polyvinyl acetal is polyvinyl butyral.
[5] The fire-resistant resin composition according to any one of [1] to [4], wherein the content of the plasticizer is 0.5 to 100 parts by mass per 100 parts by mass of the resin.
[6] The content of the thermally expandable layered inorganic material is 10 to 50 parts by mass per 100 parts by mass of the fire-resistant resin composition. [1] to [5].
[7] The fire-resistant resin composition according to any one of [1] to [6], wherein the ratio of the resin to the powder (resin/powder) is 0.2 to 3.
[8] The fire-resistant resin composition according to any one of [1] to [7], wherein the thermally expandable layered inorganic material is thermally expandable graphite.
[9] A fire-resistant material comprising the fire-resistant resin composition according to any one of [1] to [8].
[10] The fireproof material according to [9], having an expansion ratio of 5 times or more at 300°C and an expansion ratio of 20 times or more at 600°C.
[11] The fire-resistant material according to [9] or [10], having a residual hardness of 4 kgf/ ^cm2 or more at 300°C and a residual hardness of 0.3 kgf/cm2 or ^more at 600°C.
[12] The fireproof material according to any one of [9] to [11], wherein the residue maintenance rate at 300°C is 80% or more and the residue maintenance rate at 600°C is 50% or more.
[13] The fire-resistant material according to any one of [9] to [12], wherein the fire-resistant resin composition has a thermal expansion starting temperature of 100 to 300° C.
[14] The fireproof material according to any one of [9] to [13], having a thickness of 0.1 to 10 mm.
[15] A fire-resistant laminate comprising the fire-resistant material according to any one of [9] to [14], and a substrate and an adhesive layer integrated with the fire-resistant material.
[16] A compartment penetration treatment material comprising the fire-resistant material according to any one of [9] to [14] or the fire-resistant laminate according to [15].
[17] A compartment penetration treatment structure comprising the compartment penetration treatment material described in [16].
[18] A construction method for the compartment penetration structure described in [17].

The present invention provides a fire-resistant resin composition that can block the compartment penetration and inhibit the spread of fire in the event of a fire, and harden the expansion residue to maintain the blockage of the compartment penetration.

3 is a schematic cross-sectional view showing the configuration of a sheet-like member of a compartment penetration processing structure. FIG. 3 is a schematic cross-sectional view showing the configuration of a sheet-like member of a compartment penetration processing structure. FIG. 1 is a perspective view showing a partition penetration treatment structure before the partition penetration treatment material is installed. FIG. FIG. 4 is a cross-sectional view showing a compartment penetration processing structure.

The present invention will be described in detail below.
The fire-resistant resin composition of the present invention contains a resin, a plasticizer, specific additives described below, and a thermally expandable layered inorganic material.

(resin)
The fire-resistant resin composition of the present invention contains a resin containing at least one selected from the group consisting of polyvinyl acetal, polybutene, and a rubber component. By using these resins, a fire-resistant material having good fire resistance and residual hardness can be obtained. In addition, by using a rubber component, high fire resistance and residual hardness can be obtained, and by using polybutene or polyvinyl acetal, adhesion can be easily obtained. Among these, it is preferable to contain a resin containing at least one selected from the group consisting of polybutene and a rubber component.

<Polyvinyl acetal>
The polyvinyl acetal is not particularly limited as long as it is a polyvinyl acetal obtained by acetalizing polyvinyl alcohol with an aldehyde, but polyvinyl butyral (PVB) is preferred. By using polyvinyl butyral, it is possible to increase the mechanical strength even when the amount of resin relative to the fire-resistant additive is relatively small. Therefore, even if the thickness of the fire-resistant material is reduced, a certain level of mechanical strength can be ensured.
The amount of hydroxyl groups in the polyvinyl acetal is preferably 20 to 40 mol%. By making the amount of hydroxyl groups 20 mol% or more, the polarity of the polyvinyl acetal is increased, the binding force with the fire-resistant additive is strengthened, and the mechanical strength of the fire-resistant material is likely to be improved. Furthermore, by making the amount of hydroxyl groups 40 mol% or less, the fire-resistant material is prevented from becoming too hard. The amount of hydroxyl groups is more preferably 23 mol% or more, and even more preferably 26 mol% or more. Furthermore, the amount of hydroxyl groups is more preferably 37 mol% or less, and even more preferably 35 mol% or less.

The degree of acetalization of the polyvinyl acetal is preferably 40 to 80 mol%. By setting the degree of acetalization within the above range, the amount of hydroxyl groups is set within a desired range, and the mechanical strength of the fireproof material is easily improved. The degree of acetalization is more preferably 55 mol% or more, even more preferably 65 mol% or more, and more preferably 76 mol% or less.
The amount of acetyl groups in the polyvinyl acetal is preferably 0.1 to 30 mol%. When the amount of acetyl groups is within this range, the polyvinyl acetal has excellent moisture resistance, excellent compatibility with plasticizers, and exhibits high flexibility, improving handleability. By setting the amount of acetyl groups within these ranges, the amount of hydroxyl groups described above is set within a desired range, and the mechanical strength of the fireproof material is easily improved. From these viewpoints, the amount of acetyl groups is more preferably 0.2 mol% or more, even more preferably 0.5 mol% or more, and more preferably 15 mol% or less, even more preferably 7 mol% or less.
The degree of acetalization, the amount of hydroxyl groups, and the amount of acetyl groups can be measured and calculated, for example, by a method in accordance with JIS K6728 "Testing methods for polyvinyl butyral."

The degree of polymerization of the polyvinyl acetal is preferably 200 to 3000. By setting the degree of polymerization within this range, the fire-resistant additive can be appropriately dispersed in the fire-resistant material. The degree of polymerization is more preferably 250 or more, and further preferably 300 or more.
When the degree of polymerization of polyvinyl acetal is reduced, the viscosity is also reduced, the fire-resistant additive is easily dispersed in the fire-resistant material, and the mechanical strength of the fire-resistant material is improved. From such a viewpoint, the degree of polymerization of the polyvinyl acetal resin is preferably 2000 or less, more preferably 1500 or less, and further preferably 1000 or less.
The degree of polymerization of the polyvinyl acetal resin refers to a viscosity average degree of polymerization measured based on the method described in JIS K6728.

The 10% by mass ethanol/toluene viscosity of the polyvinyl acetal resin is preferably 5 mPa·s or more, more preferably 10 mPa·s or more, and even more preferably 15 mPa·s or more. The 10% by mass ethanol/toluene viscosity is preferably 500 mPa·s or less, more preferably 300 mPa·s or less, and even more preferably 200 mPa·s or less. By setting the 10% by mass ethanol/toluene viscosity of the polyvinyl acetal resin as described above, it becomes easier to disperse the fire-resistant additive in the fire-resistant material, and the mechanical strength of the fire-resistant material is improved.
The 10 mass % ethanol/toluene viscosity is a value measured as follows.
150 ml of an ethanol/toluene (weight ratio 1:1) mixed solvent is placed in an Erlenmeyer flask, and a weighed sample is added to it to make the resin concentration 10 wt %, and the solution is dissolved by shaking in a thermostatic chamber at 20° C. The solution is kept at 20° C. and the viscosity is measured using a BM type viscometer, so that the 10 mass % ethanol/toluene viscosity can be calculated.

The aldehyde is not particularly limited, but generally, an aldehyde having 1 to 10 carbon atoms is preferably used. The aldehyde having 1 to 10 carbon atoms is not particularly limited, and examples thereof include n-butylaldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, and benzaldehyde. Among these, n-butylaldehyde, n-hexylaldehyde, and n-valeraldehyde are preferred, and n-butylaldehyde is more preferred. These aldehydes may be used alone or in combination of two or more.

The resin used in the present invention may consist of polyvinyl acetal alone, but may also be used in combination with other resins. The content of polyvinyl acetal is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of the resin.

<Rubber component>
The rubber component used in the present invention is preferably at least one selected from the group consisting of ethylene propylene-based rubbers such as chloroprene rubber, natural rubber, butyl rubber, styrene-butadiene rubber, nitrile-butadiene rubber, ethylene propylene rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, and acrylic rubber. By using these rubber components in the fire-resistant resin composition, the fire resistance of the fire-resistant material made of the composition is improved. Among them, it is more preferable to contain a rubber component containing a chlorine atom, such as chloroprene rubber, chlorosulfonated polyethylene rubber, or epichlorohydrin rubber.
The rubber component preferably contains at least butyl rubber. When butyl rubber is used as the rubber component, adhesion is easily imparted to the fireproof material obtained from the composition. From the viewpoint of improving adhesion, the butyl rubber is preferably used in combination with polyvinyl acetal, polybutene, a petroleum resin described later, or a combination of two or more of these.

The content of the rubber component in the present invention is not particularly limited, but is preferably 10 to 100 parts by mass, more preferably 15 to 95 parts by mass, and even more preferably 20 to 93 parts by mass, per 100 parts by mass of the resin.
The content of the rubber component containing chlorine atoms is not particularly limited, but is preferably 0 to 80 parts by mass, more preferably 5 to 70 parts by mass, and even more preferably 10 to 65 parts by mass, per 100 parts by mass of the resin.

The rubber component used in the present invention has a Mooney viscosity ML (1+4) at 100°C of preferably 10 to 150, more preferably 20 to 140, and even more preferably 30 to 130. By having the Mooney viscosity ML (1+4) in the above range, the processability and moldability are good, making it easy to produce the desired sheet or molded body. In addition, since it is filled uniformly, good fire resistance performance can be obtained. In addition, when a rubber component containing chlorine atoms such as chloroprene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene rubber, or nitrile-butadiene rubber-PVC copolymer is contained, the chlorine content of the rubber component containing chlorine atoms is preferably 5 to 50, more preferably 8 to 45, and even more preferably 10 to 40. By making it equal to or greater than these lower limits, the fire resistance of the fire-resistant material can be improved. In addition, by making it equal to or less than these upper limits, the generation of toxic gas derived from chlorine can be suppressed when a fire occurs. In consideration of these points, it is preferable to contain butyl rubber, chloroprene rubber, or nitrile-butadiene rubber.

<Polybutene>
When polybutene is used in the present invention, it is not particularly limited, and examples thereof include homopolymers of isobutene, copolymers of isobutene and n-butene, and emulsions of polybutene. By using polybutene in the fire-resistant resin composition, the adhesion of the fire-resistant material made of the composition is improved, and the fire-resistant material can be easily attached to fittings and the like without using double-sided tape or the like during construction. Among these, copolymers of isobutene and n-butene are preferred.
The polybutene has a weight average molecular weight of, for example, 300 to 5,000, preferably 300 to 2,000, as measured by a method in accordance with ASTM D 2503.

The amount of polybutene contained is not particularly limited, but is preferably 3 to 70 parts by mass, more preferably 5 to 65 parts by mass, and even more preferably 10 to 60 parts by mass, per 100 parts by mass of resin.

The above resins may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination in order to more effectively exhibit fire resistance and residual hardness.

In the present invention, when two or more resins are used in combination, the resin combinations include polyvinyl acetal and a rubber component, polyvinyl acetal and polybutene, polyvinyl acetal, polybutene and a rubber component, and polybutene and a rubber component. Among them, it is more preferable to use a combination of polybutene and a rubber component from the viewpoint of improving the residue hardness and residue retention rate of the fireproof material.

In the present invention, when two or more kinds of resins are used in combination, the content ratio of each resin is not particularly limited. For example, when polyvinyl acetal and a rubber component are used in combination, the content of polyvinyl acetal is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, and even more preferably 120 to 180 parts by mass, per 100 parts by mass of the rubber component.
When polyvinyl acetal and polybutene are used in combination, the content of polyvinyl acetal is preferably 30 to 150 parts by mass, more preferably 40 to 120 parts by mass, and even more preferably 50 to 100 parts by mass, per 100 parts by mass of polybutene.
When polybutene and a rubber component are used in combination, the content of polybutene is preferably 5 to 300 parts by mass, more preferably 10 to 270 parts by mass, and further preferably 15 to 240 parts by mass, per 100 parts by mass of the rubber component.

The resin constituting the fire-resistant resin composition of the present invention preferably contains at least one selected from the group consisting of polyphenylene oxide and petroleum resin in addition to the above-mentioned resin. The composition may contain either one of the polyphenylene oxide and the petroleum resin, or both of them.

<Polyphenylene oxide>
The polyphenylene oxide may be an unmodified polyphenylene oxide such as poly(2,6-dimethyl-1,4-phenylene oxide) or a modified polyphenylene oxide. By using the polyphenylene oxide, the residue hardness and the residue retention rate can be improved.
When the resin contains polyphenylene oxide, the content of polyphenylene oxide is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 45 parts by mass, per 100 parts by mass of the resin, from the viewpoint of enabling adjustment of the residue hardness and residue maintenance rate of the fire-resistant material to the desired range.

In the present invention, when polyphenylene oxide is used, it is preferable to use it in combination with at least one resin selected from the group consisting of polybutene and a rubber component, and it is more preferable to use it in combination with both polybutene and a rubber component. When polyphenylene oxide is used in combination with a rubber component, it may be used in combination with a chlorine-containing rubber component or with another rubber component (a chlorine-free rubber component). By using polyphenylene oxide, it is possible to improve the residue hardness and residue retention rate of the fire-resistant material and ensure sufficient fire resistance, even without using a chlorine-containing rubber component.

<Petroleum resin>
Examples of the petroleum resin include aliphatic hydrocarbon resin-based petroleum resin, aromatic hydrocarbon resin-based petroleum resin, alicyclic saturated hydrocarbon resin-based petroleum resin, copolymer-based petroleum resin, hydrogenated petroleum resin, petroleum resin emulsion, etc. By using the petroleum resin, the adhesion of the fireproof material can be improved, and good workability can be obtained.
When the resin contains a petroleum resin, the content of the petroleum resin is preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 4 to 10 parts by mass, per 100 parts by mass of the resin, from the viewpoint of improving the adhesion of the fire-resistant material and obtaining good workability.

(Plasticizer)
The fire-resistant resin composition of the present invention contains a plasticizer. The inclusion of a plasticizer imparts flexibility to the composition, which makes it easier to uniformly mix the components of the composition during production of the composition, and as a result, the residue hardness and residue retention rate of the fire-resistant material made of the composition can be adjusted to a desired range. In addition, good workability is obtained, and the composition is more likely to expand in the event of a fire, improving fire resistance.
Specific examples of the plasticizer include phthalate plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP); adipate esters such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA); dibutoxyethyl adipate, di(butoxyethoxyethyl) adipate, di(methoxytetraethylene glycol) adipate, di(methoxypentaethylene glycol) adipate, and other plasticizers. Examples of suitable plasticizers include adipic acid ether ester plasticizers such as dipic acid (methoxytetraethylene glycol) (methoxypentaethylene glycol), fatty acid ester plasticizers such as adipic acid polyester, epoxidized ester plasticizers such as epoxidized soybean oil, polyether ester plasticizers, trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM), phosphate ester plasticizers such as trimethyl phosphate (TMP) and triethyl phosphate (TEP), and process oils such as mineral oil.

The plasticizers used in the present invention are, from the viewpoint of preventing crystallization of the resin and imparting flexibility, plasticizers having an ester structure, namely, phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP), adipate esters such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA), and dibutoxyethyl adipate, di(butoxyethoxyethyl) adipate, di(methoxytetraethylene glycol) adipate, and di( At least one selected from the group consisting of adipic acid ether ester plasticizers such as adipic acid (methoxypentaethylene glycol), adipic acid (methoxytetraethylene glycol) (methoxypentaethylene glycol), fatty acid ester plasticizers such as adipic acid polyester, epoxidized ester plasticizers such as epoxidized soybean oil, polyether ester plasticizers, trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM), and phosphate ester plasticizers such as trimethyl phosphate (TMP) and triethyl phosphate (TEP) are preferred.

Among the plasticizers having an ester structure, at least one selected from the group consisting of plasticizers further having an ether structure, that is, polyether ester plasticizers and adipate ether ester plasticizers such as dibutoxyethyl adipate, di(butoxyethoxyethyl adipate), di(methoxytetraethylene glycol) adipate, di(methoxypentaethylene glycol) adipate, and (methoxytetraethylene glycol)(methoxypentaethylene glycol) adipate, is more preferred.
In the present invention, the plasticizers may be used alone or in combination of two or more.

When the fire-resistant resin composition contains a plasticizer, the content of the plasticizer in the fire-resistant resin composition is, for example, in the range of 0.5 parts by mass to 100 parts by mass, preferably in the range of 1 part by mass to 80 parts by mass, more preferably in the range of 10 parts by mass to 70 parts by mass, and even more preferably in the range of 20 parts by mass to 50 parts by mass, relative to 100 parts by mass of the resin component. When the plasticizer is at or above these lower limits, flexibility is imparted and moldability tends to be good. Furthermore, when the plasticizer is at or below the upper limits, appropriate strength is imparted to the molded body. Furthermore, when the content is within the above range, it is easy to adjust the residue hardness and residue retention rate of the fire-resistant material to the desired range.

(Thermal Expandable Layered Inorganic Material)
The thermally expandable layered inorganic material is a conventionally known material that expands when heated, and examples thereof include vermiculite and thermally expandable graphite, among which thermally expandable graphite is preferred. The thermally expandable layered inorganic material may be in the form of particles or scales. The thermally expandable layered inorganic material expands when heated to form large-capacity voids, and therefore the fireproof material using the thermally expandable layered inorganic material of the present invention suppresses the spread of fire and extinguishes the fire when ignited.
Thermally expandable graphite is produced by treating powders of natural flake graphite, pyrolytic graphite, kish graphite, etc. with inorganic acids such as concentrated sulfuric acid, nitric acid, selenic acid, etc., and strong oxidizing agents such as concentrated nitric acid, perchloric acid, perchlorates, permanganates, dichromates, hydrogen peroxide, etc., to produce a graphite intercalation compound. The produced thermally expandable graphite is a crystalline compound that maintains the layered structure of carbon.
The thermally expandable graphite used in the present invention may be thermally expandable graphite obtained by treating with an acid and then neutralizing the same with ammonia, aliphatic lower amines, alkali metal compounds, alkaline earth metal compounds, or the like.
Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine.
Examples of the alkali metal compounds and alkaline earth metal compounds include hydroxides, oxides, carbonates, sulfates, and organic acid salts of potassium, sodium, calcium, barium, magnesium, and the like.

The particle size of the thermally expandable graphite is preferably 20 to 200 mesh. When the particle size of the thermally expandable graphite is within the above range, it expands and easily creates large-capacity voids, improving fire resistance. Also, dispersibility in resin is improved.
The average aspect ratio of the thermally expandable graphite is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. There is no particular upper limit to the average aspect ratio of the thermally expandable graphite, but from the viewpoint of preventing cracking of the thermally expandable graphite, it is preferably 1,000 or less. When the average aspect ratio of the thermally expandable graphite is 2 or more, it becomes easier to expand and form large-capacity voids, thereby improving flame retardancy.
The average aspect ratio of the thermally expandable graphite is determined by measuring the maximum dimension (major axis) and the minimum dimension (minor axis) of each of 10 pieces of thermally expandable graphite, and averaging the values obtained by dividing the maximum dimension (major axis) by the minimum dimension (minor axis). The major axis and minor axis of the thermally expandable graphite can be measured, for example, using a field emission scanning electron microscope (FE-SEM).

In addition, the content of the thermally expandable layered inorganic material in the fire-resistant resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, relative to 100 parts by mass of the fire-resistant resin composition. In addition, the content of the thermally expandable layered inorganic material is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 48 parts by mass or less. If it is equal to or more than the above lower limit, sufficient thermal expansion can be obtained, and it is possible to sufficiently block the partition penetration part. In addition, in the present invention, even if the thermally expandable layered inorganic material is highly filled, the hardness of the expansion residue is high, and it is relatively easy to maintain fire resistance. On the other hand, if it is equal to or less than the above upper limit, the moldability is good, and the surface property, mechanical properties, flexibility, etc. of the sealing member are also good. In addition, by selecting the content of the thermally expandable graphite within the above range, it is easy to adjust the expansion ratio within the desired range.

(Specific Additives)
The fire-resistant resin composition of the present invention contains, as a specific additive, at least one selected from a flame retardant, a heat absorbing agent, a lubricant, and an inorganic filler, in addition to the above-mentioned thermally expandable layered inorganic material. Each of these components may be used alone or in combination of two or more. By containing the specific additive, the fire-resistant resin composition of the present invention can increase the residual hardness and residual retention rate of the fire-resistant resin composition.

<Flame retardants>
The flame retardant, the heat absorbing agent, and the inorganic filler are fire resistance additives, and improve the fire resistance of the fire resistant resin composition.
The flame retardant used in the present invention may include a phosphorus atom-containing compound. Examples of the phosphorus atom-containing compound include red phosphorus, various phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate, metal phosphates such as sodium phosphate, potassium phosphate, and magnesium phosphate, metal phosphite such as sodium phosphite, potassium phosphite, magnesium phosphite, and aluminum phosphite, and ammonium polyphosphate. By using these phosphorus-containing compounds, the fire-resistant resin composition can be given appropriate fire resistance and fire extinguishing performance. The flame retardant may be used alone or in combination of two or more.
Among these flame retardants, ammonium polyphosphate, aluminum phosphite, etc. are particularly preferred from the viewpoint of improving the fire resistance and fire extinguishing performance of the fire-resistant resin composition.

The flame retardant is preferably a solid at room temperature (23°C) and normal pressure (1 atm). The average particle size of the flame retardant is preferably 1 to 200 μm, more preferably 1 to 60 μm, even more preferably 3 to 40 μm, and even more preferably 5 to 20 μm. When the average particle size of the flame retardant is within the above range, the dispersibility of the flame retardant in the fire-resistant resin composition is improved, and the flame retardant can be uniformly dispersed in the resin and the amount of the flame retardant mixed into the resin can be increased.

The content of the flame retardant in the present invention is not particularly limited, but is preferably 15 to 60 parts by mass, more preferably 20 to 55 parts by mass, and even more preferably 25 to 50 parts by mass, per 100 parts by mass of resin.

<Heat absorbing agent>
A suitable example of the heat absorbing agent used in the fire-resistant resin composition of the present invention is a hydrated metal compound. A hydrated metal compound is a compound that decomposes upon contact with flame to generate water vapor and has the effect of absorbing heat. Examples of the hydrated metal compound include metal hydroxides and hydrates of metal salts. Specific examples include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium-magnesium hydroxide, hydrotalcite, boehmite, talc, dawsonite, hydrates of calcium sulfate, hydrates of magnesium sulfate, and zinc borate [ _{2ZnO.3B 2} O 5.3.5H ₂ O].
Among these, from the viewpoints of fire resistance, fire extinguishing performance, etc., at least one selected from aluminum hydroxide, magnesium hydroxide, calcium sulfate dihydrate, and magnesium sulfate heptahydrate is preferred, with aluminum hydroxide and magnesium hydroxide being particularly preferred.

The endothermic agent preferably has a thermal decomposition start temperature of 500° C. or less and an endothermic amount of 500 J/g or more. When either the thermal decomposition start temperature or the endothermic amount is within the above range, the fire can be extinguished quickly in the event of ignition. From the above viewpoints, the thermal decomposition start temperature of the endothermic agent is preferably 400° C. or less, more preferably 300° C. or less. In addition, the thermal decomposition start temperature of the endothermic agent is usually 100° C. or more, preferably 150° C. or more, and more preferably 180° C. or more. By setting the temperature at or above these lower limits, the endothermic agent is prevented from functioning erroneously due to heating other than fire.
The thermal decomposition onset temperature can be measured by a thermogravimetric differential thermal analyzer (TG-DTA), specifically, by the method described in the examples.

The endothermic amount of the endothermic agent is preferably 600 J/g or more, more preferably 900 J/g or more. When the endothermic amount of the endothermic agent is within the above range, the heat absorption is improved, so that the fire resistance and fire extinguishing performance are better. The endothermic amount of the endothermic agent is usually 4000 J/g or less, preferably 3000 J/g or less.
The endothermic heat can be measured using a thermogravimetric differential thermal analyzer (TG-DTA), specifically, by the method described in the examples.

The heat absorbing agent preferably has an average particle size of 0.1 to 90 μm. By setting the average particle size within the above range, the heat absorbing agent is easily dispersed in the resin, making it easier to incorporate a large amount of the heat absorbing agent, and making it easier to improve fire resistance and fire extinguishing performance.
From the above viewpoints, the average particle size of the heat-absorbing agent is more preferably 0.5 to 60 μm, further preferably 0.8 to 40 μm, and even further preferably 0.8 to 10 μm.

The content of the heat absorbing agent in the present invention is not particularly limited, but is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 12 to 20 parts by mass, per 100 parts by mass of the resin.

<Lubricant>
A lubricant may be used in the fire-resistant resin composition of the present invention. The composition has good fluidity by using a lubricant, and the thermally expandable layered inorganic material and the fire-resistant additive are appropriately dispersed in the composition. Therefore, the fire-resistant material made of the composition has good thermal expansion and residual hardness, and the fire resistance of the fire-resistant material is improved. Examples of the lubricant used in the present invention include resin-based lubricants and phosphate-based lubricants. It is preferable to use the lubricant in combination with the above-mentioned fire-resistant additive.

As the resin-based lubricant, any known resin-based lubricant can be used, with acrylic oligomers being preferred.
As the acrylic oligomer, an acrylic ester oligomer is preferred. Examples of the acrylic ester constituting the oligomer include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Of these, butyl acrylate oligomers are preferred. As the resin lubricant, commercially available products can be used, for example, "ADEKA STAB FC-113" manufactured by ADEKA Corporation.

Examples of phosphate lubricants include long-chain aliphatic phosphate compounds, and long-chain monoalkyl phosphates, long-chain dialkyl phosphates, etc. can be preferably used. The alkyl groups constituting the long-chain monoalkyl phosphates and long-chain dialkyl phosphates preferably have 12 to 18 carbon atoms. Examples of alkyl groups having 12 to 18 carbon atoms include dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, and octadecyl groups.
The long-chain aliphatic phosphate compound used in the present invention is preferably at least one selected from the group consisting of monododecyl phosphate, didodecyl phosphate, monooctadecyl phosphate, and dioctadecyl phosphate, and more preferably monooctadecyl phosphate, dioctadecyl phosphate, or a mixture thereof.
The lubricant used in the present invention may be one type alone or two or more types in combination. For example, a resin-based lubricant and a phosphate-based lubricant may be used in combination. Among the above, it is more preferable to use an acrylic oligomer and a long-chain aliphatic phosphate-based compound in combination.
The content of the lubricant in the fire-resistant resin composition of the present invention is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 8 parts by mass, and even more preferably 0.5 to 4 parts by mass, based on 100 parts by mass of the resin.

<Inorganic filler>
Inorganic fillers that can be used in the fire-resistant resin composition of the present invention include inorganic fillers other than the above-mentioned thermally expandable layered inorganic materials, flame retardants, heat-absorbing agents, and lubricants, and are not particularly limited. Examples of the inorganic fillers that can be used in the fire-resistant resin composition of the present invention include, but are not limited to, silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawnnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, clay, Examples of suitable materials include mica, montmorillonite, bentonite, activated clay, seviolite, imogolite, sericite, glass fiber, glass beads, silica balloon, aluminum nitride, aluminum phosphite, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconium titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dewatered sludge.
Among these, calcium carbonate and carbon black are preferred. These inorganic fillers may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the content of the inorganic filler is low, a small particle size is preferable from the viewpoint of improving dispersibility, whereas when the content is high, a large particle size is preferable because the viscosity of the fire-resistant resin composition increases and the moldability decreases as the content increases.
The average particle diameters of the flame retardant, heat absorbing agent, and inorganic filler described above are median diameter (D50) values measured by a laser diffraction/scattering type particle size distribution measuring device.

The content of the inorganic filler in the present invention is not particularly limited, but is preferably 5 to 80 parts by mass, more preferably 8 to 70 parts by mass, and even more preferably 10 to 65 parts by mass, per 100 parts by mass of the resin.

The content of the specific additive in the fire-resistant resin composition of the present invention is preferably 3 to 250 parts by mass, more preferably 5 to 200 parts by mass, even more preferably 10 to 150 parts by mass, and even more preferably 50 to 130 parts by mass, per 100 parts by mass of the resin. When the content of the specific additive is equal to or greater than the lower limit, flame retardancy is obtained and mechanical properties can be improved. On the other hand, when the content is equal to or less than the upper limit, the relative amount of the thermally expandable layered inorganic material is sufficient, and when a fire occurs, the material expands due to the flame, blocking the compartment penetration and suppressing the spread of the fire.

In addition, by using a relatively large amount of polyphenylene oxide, the amount of the specific additive can be relatively small. In this case, the content of the specific additive is preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of resin, and the content of the polyphenylene oxide is preferably 20 to 60 parts by mass, more preferably 30 to 50 parts by mass, per 100 parts by mass of resin.

The specific additives described above may have at least one selected from a flame retardant, a heat absorbing agent, a lubricant, and an inorganic filler, as described above. Among these, the combination of fire-resistant additives is preferably at least one selected from a flame retardant, a heat absorbing agent, and an inorganic filler, from the viewpoint of improving the fire resistance of the fire-resistant material, and more preferably a combination of a flame retardant and a heat absorbing agent, or a combination of a flame retardant and an inorganic filler, and it is also preferable to use a combination of a flame retardant, a heat absorbing agent, and an inorganic filler. In addition, a lubricant may be further added to each of these combinations.
Among them, a combination of ammonium polyphosphate (APP) as the flame retardant and calcium carbonate as the inorganic filler is preferred. This is believed to be due to the fact that the reaction between ammonium polyphosphate and calcium carbonate when heated by fire or the like hardens the residue. In addition, from the viewpoint of hardening the residue, it is also preferred to use aluminum phosphite as the fire-resistant additive.

In the fire-resistant resin composition of the present invention, the ratio of the resin content to the powder content (resin/powder) is preferably 0.2 to 3, more preferably 0.5 to 2, and even more preferably 0.5 to 0.7. By setting the ratio of the resin content to the powder content in the above range, it becomes easy to adjust the residue hardness and residue maintenance rate of the fire-resistant material to the desired range.
The powder is a material that is solid at room temperature (23° C.) and normal pressure (1 atm), and is present in the fire-resistant resin composition in the form of powder, particles, or fibers without being dissolved or compatible with the resin. Specifically, among the above-described components, the solid flame retardant, heat-absorbing agent, inorganic filler, lubricant, and thermally expandable layered inorganic material are in the form of powder.

Additives that are commonly used in thermally expandable resin compositions, such as heat stabilizers, processing aids, antioxidants, antistatic agents, pigments, crosslinking agents, and crosslinking accelerators, may be added to the fire-resistant resin composition of the present invention as necessary, provided that the physical properties of the composition are not impaired. Of these, it is preferable to use processing aids.

[Fireproof material]
The fire-resistant material of the present invention is preferably made of the fire-resistant resin composition of the present invention, and is particularly preferably in the form of a sheet. The thickness of the fire-resistant material is preferably 0.1 to 10 mm, more preferably 2 to 8 mm, and even more preferably 3 to 5 mm. When the thickness is equal to or greater than the lower limit, sufficient fire resistance is ensured, and when the thickness is equal to or less than the upper limit, flexibility of the fire-resistant material is ensured.

The thermal expansion start temperature of the fireproof material of the present invention is not particularly limited, but is preferably 100 to 300° C., more preferably 120 to 280° C., and even more preferably 130 to 250° C. By setting the temperature at or above these lower limits, the thermally expandable material is prevented from accidentally expanding due to heating other than fire. By setting the temperature at or below the upper limits, the thermally expandable material is more likely to expand reliably due to heating from fire.
The method for measuring the thermal expansion starting temperature of the fireproof material of the present invention is as described in the Examples below.

The expansion ratio of the fireproof material of the present invention at 300° C. is preferably 5 times or more, more preferably 10 times or more, and even more preferably 15 times or more. The expansion ratio at 600° C. is preferably 20 times or more, more preferably 25 times or more, and even more preferably 30 times or more. When the expansion ratio of the fireproof material is equal to or more than the above lower limit, the expansion performance at the time of fire occurrence is good, and the effect of blocking the compartment penetration part and preventing the fire from spreading can be fully exhibited.
The expansion ratio of the fireproof material is not particularly limited, but from the viewpoint of ensuring a certain residue hardness and residue maintenance rate in the event of a fire and preventing the occurrence of gaps between the fireproof material and the compartment penetration part, it is preferably 50 times or less, more preferably 40 times or less, even more preferably 35 times or less, and even more preferably 20 times or less at 300° C. Furthermore, it is preferably 65 times or less, more preferably 60 times or less, even more preferably 50 times or less, and even more preferably 40 times or less at 600° C.

The residual hardness of the fireproof material of the present invention at 300° C. is preferably 3 kgf/cm ² or more, more preferably 4 kgf/cm ² or more, and even more preferably 5 kgf/cm ² or more. The residual hardness at 600° C. is preferably 0.1 kgf/cm ² or more, more preferably 0.2 kgf/cm ² or more, and even more preferably 0.3 kgf/cm ² or more. By having a residual hardness of at least the above lower limit, the fireproof material can be prevented from being blown away by the flames when a fire occurs, and the spread of fire when a fire occurs can be effectively prevented.
The residual hardness of the fireproof material is not particularly limited, but is preferably 50 kgf/cm2 ^{or less} , more preferably 40 kgf/ ^cm2 or less, and even more preferably 20 kgf/ ^cm2 or less at 300°C. Also, at 600°C, it is preferably 10 kgf/cm2 or ^less , more preferably 4 kgf/ ^cm2 or less, and even more preferably 2 kgf/ ^cm2 or less.

The residue maintenance rate of the fireproof material of the present invention at 300° C. is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. Also, the residue maintenance rate at 600° C. is preferably 40% or more, more preferably 44% or more, and even more preferably 50% or more. When the residue maintenance rate is equal to or more than the above lower limit, excellent fire resistance can be obtained and the spread of fire in the event of a fire can be effectively prevented.
The residue retention rate of the refractory material is not particularly limited, but is preferably 95% or less, more preferably 93% or less, at 300° C., and is preferably 70% or less, more preferably 65% or less, at 600° C.
The expansion ratio, residue hardness, and residue retention rate of the fireproof material can be measured by the method described in the Examples.

[Fire-resistant laminate]
The fireproof material of the present invention may be used as a single layer of fireproof material, or may be used as a multilayer body (fireproof laminate) by laminating two or more layers of fireproof material (hereinafter also referred to as fireproof material layer) or laminating layers other than fireproof material. Examples of the other layers used include a substrate, a pressure-sensitive adhesive layer, etc.
The fire-resistant laminate may have both a substrate and a pressure-sensitive adhesive layer, but it is sufficient to have at least one of them.

<Substrate>
The substrate used in the fireproof laminate supports the fireproof material, and depending on the material, transfers heat evenly to the fireproof material. Examples of the substrate include metal foils such as aluminum foil and copper foil, metal foil composites such as glass cloth and aluminum glass cloth composites of metal foil and glass cloth, paper, cloth, and resin film. Among these, from the viewpoint of fire resistance, it is preferable to be composed of a non-combustible material, and metal foil and metal foil composites are more preferable. By using metal foil and metal foil composites, it becomes easier to transfer heat evenly to the fireproof material, and when a fire occurs, the fireproof material is evenly foamed, making it easier to improve fire resistance. In addition, the non-combustible material is defined in the Building Standards Act and the Building Standards Act Enforcement Order.

The base material may be provided on one side of the fire-resistant material, or on both sides so as to sandwich the fire-resistant material. However, it is preferable that the base material be provided on both sides of the fire-resistant material, from the viewpoint of effectively controlling the expansion of the fire-resistant material with the base material and expanding it in the direction of the compartment penetration, thereby ensuring that the compartment penetration is closed in the event of a fire.

The thickness of each substrate is not particularly limited, but is, for example, 0.01 to 1 mm, and preferably 0.05 to 0.5 mm. By making the noncombustible material layer have a thickness below these upper limits, flexibility is imparted to the sheet-like member. Also, by making the thickness above the lower limits, fire resistance is more easily ensured.

<Adhesive Layer>
The adhesive layer used in the fire-resistant laminate may be formed of an adhesive, and examples of the adhesive that can be used include acrylic adhesives, urethane adhesives, rubber adhesives, and silicone resin adhesives. The adhesive layer may be non-flammable, semi-non-flammable, or flame-retardant, and a flame retardant may be blended into the adhesive used. The thickness of the adhesive layer is, for example, 5 to 400 μm, and preferably 10 to 150 μm.
The pressure-sensitive adhesive layer may also be disposed on the outermost surface of the fire-resistant laminate so as to be able to adhere the fire-resistant laminate to other members.

As mentioned above, multiple sheet-like fire-resistant materials may be laminated. When multiple sheet-like fire-resistant materials are laminated, if they have adhesive properties, they may be laminated directly or via an adhesive layer made of a known adhesive other than an adhesive layer.

When a plurality of sheet-shaped fireproof materials are laminated, it is preferable that the layers have different expansion ratios, and it is advisable to control the expansion ratio according to the usage form. When two or more layers of sheet-shaped fireproof materials are provided, it is preferable that at least one of the layers is made of the fireproof resin composition of the present invention and constitutes a fireproof material layer having a high expansion ratio.
In addition, in a fire-resistant laminate composed of a substrate and a fire-resistant material layer, the substrate may have two or more layers, and further, if the fire-resistant material layer has adhesive properties, it is preferable to arrange it on the outermost surface so that it can be adhered to other members.

The fireproof laminate preferably has a substrate and a fireproof layer. The fireproof laminate may be two layers of the substrate and the fireproof layer, or may be at least three layers of the substrate and the fireproof layer stacked alternately. Furthermore, the fireproof laminate is not limited to a three-layer structure, and may be four layers of the substrate and the fireproof layer stacked alternately, or may be more than four layers.
The fire-resistant material layer obtained from the fire-resistant resin composition of the present invention has a high expansion ratio and the residue is hard, so that it may constitute a part or all of the layers among a plurality of fire-resistant material layers.
The detailed configuration of the fire-resistant laminate will be described later.

It is also preferable that the fireproof laminate is formed by alternately stacking at least three layers of substrates and thermally expandable fireproof layers. Specifically, the fireproof laminate 3 may be formed by alternately stacking three layers of substrates 30A, 30B and fireproof layers 31A as shown in FIG. 1(a), or may be formed by alternately stacking three layers of substrate 30A and fireproof layers 31A, 31B as shown in FIG. 1(b). The sheet-like member 3 is not limited to a three-layer structure, and may be formed by alternately stacking four layers of substrates 30A, 30B and fireproof layers 31A, 31B as shown in FIG. 1(c).

In addition, when the substrate and the fireproofing layer are laminated alternately, the substrate and the fireproofing layer do not have to be alternately arranged one by one, as long as the sheet-like member 3 has the substrate/fireproofing layer/substrate or the fireproofing layer/substrate/fireproofing layer in this order, and the same type of layers may be laminated continuously, such as substrate/substrate/fireproofing layer/fireproofing layer. For example, as shown in FIG. 1(d), substrates 30A and 30B may be laminated continuously, and substrates 30B and 30C and fireproofing layer 31A may be laminated alternately. In addition, as shown in FIG. 1(e), the sheet-like member 3 may have no limit to the number of layers, and a plurality of substrates 30A, ... 30Y, 30Z and a plurality of fireproofing layers 31A, ... 31Y, 31Z may be laminated alternately in multiple layers.

As shown in FIG. 2(a), it is also preferable that the fireproof laminate 3 has an adhesive fireproof material layer 31A disposed on the outermost surface.
In addition, when an adhesive layer is provided, it is also preferable to configure the fireproof material layer 31A provided with the adhesive layer 33 on the outermost surface as shown in Fig. 2(b) . In this case, the fireproof performance of the fireproof material layer itself can be easily improved by relatively increasing the content of chloroprene rubber, polyphenylene oxide, or the like as the resin, or by increasing the content of the thermally expandable layered inorganic material.

The above configuration allows the fire-resistant laminate 3 to be easily fixed to other members such as the partition 11 (see FIG. 3) described below without using a fixing member separate from the fire-resistant laminate 3. In addition, by making the fire-resistant layer itself adhesive, it is not necessary to provide an adhesive layer, so the configuration of the fire-resistant laminate 3 can be further simplified. Note that when the fire-resistant laminate 3 has an adhesive fire-resistant layer or an adhesive layer on its outermost surface, a release sheet may be attached to the outermost surface. The release sheet may be peeled off from the outermost surface when in use.

It should be noted that the fire-resistant laminate shown in FIG. 2 is only one example, and the configuration in the case where an adhesive layer is provided as the outermost layer, or an adhesive fire-resistant layer is provided as the outermost layer, is not limited to the configuration shown in FIG. 2, and may be a two-layer structure of fire-resistant agent layer/substrate, or a three-layer structure of substrate/fire-resistant agent layer/substrate/adhesive layer, or a three-layer structure of substrate/fire-resistant agent layer/adhesive layer, etc.
In the multi-layer structure, the sheet-like member 3 may have the same layer structure throughout, or may have a partially different structure. For example, the layer structure between the base material and the fireproof material layer may be partially changed.

<Production Method>
The fire-resistant resin composition of the present invention can be produced, for example, as follows. First, a specific additive such as a fire-resistant additive in a predetermined amount, a thermally expandable layered inorganic material, a resin, and other additives that are blended as necessary are mixed in a mixer such as a kneading roll to obtain a fire-resistant resin composition. The temperature during mixing is preferably 100 to 150°C. By setting the temperature during mixing to the lower limit or higher, it becomes easier to mix each component uniformly. In addition, by setting the temperature during mixing to the upper limit or lower, it is possible to prevent the thermally expandable layered inorganic material from expanding during mixing, and a good quality fire-resistant material can be provided. The fire-resistant resin composition may be diluted by adding a solvent as appropriate.

The fire-resistant resin composition obtained as described above may be molded into a predetermined shape to form a fire-resistant material. Specifically, the fire-resistant material may be formed into a sheet-like fire-resistant material by extrusion molding, press molding, or the like. The fire-resistant resin composition diluted with a solvent may be applied to a support such as a substrate or a release sheet, and then appropriately dried to form a fire-resistant material on one side of the support. The fire-resistant material formed on the release sheet may be peeled off from the release sheet to form a sheet-like fire-resistant material consisting of a single layer of fire-resistant material.
Alternatively, the laminate may be peeled off from the release sheet and then laminated on another layer to obtain a multi-layered fireproof laminate, or may be laminated on another layer while still on the release sheet or on another support.

The fire-resistant resin composition of the present invention is used in fireproof structures for buildings, and is particularly preferably used in fireproof structures for compartment penetrations in partitions such as walls for passing long inserts such as cables, piping, etc. That is, it is preferably used as a fireproof material in a compartment penetration for preventing the spread of fire to other compartments when a fire breaks out in one of the compartments.
The fire-resistant resin composition of the present invention can also be suitably used as a compartment penetration treatment material in a compartment penetration treatment structure.

[Compartment penetration processing structure]
Hereinafter, specific examples in which the fire-resistant resin composition of the present invention is applied as a fire-resistant material to a compartment penetration treatment structure will be described in detail with reference to the drawings.
As shown in FIG. 3, the compartment penetration structure is a compartment penetration structure in which a compartment penetration part 15, which is formed in a partition part 11 of a building and through which a long insert 21 is inserted, has a fire-resistant structure.
In the compartment penetration structure, the fireproof material is applied as a sheet-like member 3 to the compartment penetration portion 15 and is used as at least a part of the compartment penetration material for forming the compartment penetration structure 10.
In this specification, as shown in Figure 3, the components (such as the sheet-like member 3 and the fixing members for fixing these) that are applied to the partition penetration portion 15 to form the partition penetration treatment structure 10 are collectively referred to as the partition penetration treatment material.

The partition 11 in the partition penetration processing structure is a member that separates partitions (first partition A and second partition B) on the wall surface of a building, and has a partition penetration part 15 that penetrates from one outer surface 11A side of the partition 11 to the other outer surface 11B side. The partition 11 shown in FIG. 3 is a hollow wall, and is composed of two wall materials (partition materials) 12A, 12B arranged with a gap (hollow part 13). Therefore, the partition penetration part 15 is composed of a through hole 13A formed in one wall material 12A, a through hole 13B formed in the other wall material 12B, and a hollow part 13 between them. The outer surface of one wall material 12A constitutes the outer surface 11A of the partition 11, and the outer surface of the other wall material 12B constitutes the outer surface 11B of the partition 11. The through holes 13A, 13B may have, for example, a circular shape, an elliptical shape, or a shape similar thereto. In addition, the through holes 13A and 13B on the outer surfaces 11A and 11B, respectively, form the openings 13C and 13D of the partition through-hole 15 provided in the partition 11.

The configuration of the partition penetration processing structure on one side of the opening 13C of the partition section 11 is described below, but in this embodiment, the configuration of the partition penetration processing structure on the other side of the opening 13D is similar, so the description is omitted.

The compartment penetration treatment structure 10 includes a sheet-like member 3 and a cover member 5 as compartment penetration treatment materials, and the sheet-like member 3 is a fireproof material in which a base material and a fireproof material layer are integrated as described above. The sheet-like member 3 is a member that includes the fireproof material described above, and may be composed of a single layer of fireproof material, but FIG. 3 shows a structure that is a fireproof laminate.

[Sheet-like member]
As shown in Fig. 3, the fireproof material (sheet-like member 3) has slits 32 through which the insert 21 is inserted, and at least one of the slits 32 extends to the outer edge of the sheet-like member 3. The slits 32 are formed by cutting. The sheet-like member 3 allows the insert 21 to be inserted into the inside of the sheet-like member 3 through the slits 32 extending to the outer edge. The slits 32 may have a form having a hole through which the insert 21 is inserted and a slit 32 extending from the hole to the outer edge of the sheet-like member 3.

As shown in FIG. 4, the sheet-like member 3 with the insert 21 inserted through the slit 32 is placed on the outer surface 11A so as to cover the gap 13E between the opening 13C and the insert 21 from the outside of the partition 11, thereby blocking the gap 13E between the opening 13C and the insert 21 with the sheet-like member 3. It is preferable that the sheet-like member 3 is placed so as to be in contact with both the outer surface 11A of the partition 11 and the outer periphery of the insert 21. By placing the sheet-like member 3 so as to be in contact with the insert 21 and the partition 11, the opening 13C of the partition 11 can be blocked, and the fire resistance can be improved and maintained.

The details of the sheet-like member 3 (fire-resistant material or fire-resistant laminate) are as described above, but by using the sheet-like member 3, a fire-resistant structure is formed without placing filler such as fire-resistant putty, rock wool, etc. inside the compartment penetration part 15, so there is no variation depending on the worker.
Furthermore, when multiple fireproof layers are laminated on the sheet-like member 3, the fireproof layer on the side of the expanded partition 11 is embedded in the gap 13E, preventing the sheet-like member 3 from moving away from the partition 11 when it expands, making the above-mentioned displacement less likely to occur. On the other hand, it is preferable that the fireproof layer located away from the partition 11 expands evenly, and the expansion residue can appropriately prevent the spread of fire.

When the sheet-like member 3 has a plurality of fireproof layers, it is preferable that the expansion ratio of the fireproof layer farthest from the outer surface 11A of the partition 11 is higher than that of the fireproof layer closest to the outer surface 11A of the partition 11. That is, in the sheet-like member 3 in Fig. 1 (b) and (c), if the right side of the figure is the partition 11 side, it is preferable that the expansion ratio of the fireproof layer 31B is higher than that of the fireproof layer 31A. At least the fireproof layer 31B is preferably made of the fireproof resin composition of the present invention. The fireproof resin composition of the present invention can have a high expansion ratio, so it is suitable as a material for the fireproof layer 31B.
In this way, when the expansion ratio of the fireproof material layer on the partition 11 side is low, the strength of the expansion residue is maintained high, the fireproof material layer embedded in the gap 13E properly supports the sheet-like member 3, and the occurrence of displacement becomes even less likely. Also, the fireproof material layer located away from the partition 11 expands sufficiently by heating, and is likely to exhibit higher fire resistance.

When there are three or more fireproof layers, it is preferable to increase the expansion ratio of the fireproof layers that are further from the outer surface 11A of the partition 11 in order to expand the fireproof layers more uniformly.

When the sheet-like member 3 has an adhesive fire-resistant material layer 31A disposed on its outermost surface as shown in FIG. 2( a ), the sheet-like member 3 can be adhered to the outer surface 11A of the partition portion 11 by the adhesive fire-resistant material layer.
In addition, as shown in FIG. 2(b), in the case where the fireproof material layer 31A having the adhesive layer 33 is arranged on the outermost surface, it is sufficient to adhere it to the outer surface 11A of the partition portion 11 by the adhesive layer.
In addition, the sheet-like member 3 may be fixed to the outer surface 11A of the partition portion 11 by a fixing member, such as a tacker or a screw, which is a separate member from the sheet-like member 3. Of course, the sheet-like member 3 may be fixed to the partition portion 11 by a combination of two or more of these fixing members.

[Cover member]
The cover member 5 is provided so as to be connected to the sheet-like member 3, and is a member that covers the sheet-like member 3 provided in the partition section 11. For example, as shown in FIG. 3, four cover members 5 are used so as to be connected to the four edges of the sheet-like member 3, and four extension parts extending outward from the sheet-like member 3 are used, and as shown in FIG. 4, the cover member 5 covers the sheet-like member 3 provided in the partition section 11. Examples of means for providing the cover member 5 so as to be connected to at least a part of the sheet-like member 3 include means for fixing the cover member 5 by known fixing means such as adhesives, pressure-sensitive adhesives, and adhesive tapes, as well as fixing members such as tackers and screws. Here, the adhesives, pressure-sensitive adhesives, and adhesive tapes are preferably made of a non-combustible material, a semi-non-combustible material, or a flame-retardant material, and it is preferable to blend a flame retardant or the like into the adhesives, pressure-sensitive adhesives, etc.
The cover member 5 is sheet-like and deformable, so that it can easily cover the sheet-like member 3 .

As shown in FIG. 4, the cover member 5 has a portion covering the opening 13C of the partition penetration portion 15 that surrounds the insert 21 so as to be in contact with it, and is fixed to the insert 21 by a string-like member 22 wound around it from the outside. The string-like member 22 may be any bendable member, and is preferably a wire member that includes a wire. The wire member may be a metal wire alone, or a resin-coated wire such as Nejirikko (registered trademark) in which a metal wire is coated with resin, or a wire and fiber entangled such as a wire mould. When a wire member is used, the cover member 5 can be fixed to the insert 21 simply by twisting or twisting it.

The cover member 5 may cover a part of the sheet-like member 3 so that the part of the sheet-like member 3 cannot be seen from the outside. Specifically, the cover member 5 may cover a part of the sheet-like member 3 through which the insert 21 is inserted, thereby improving the design of the compartment penetration part 15 and the fire resistance of the compartment penetration part 15.
On the other hand, the cover member 5 may cover a part of the sheet-like member 3 so as to be visible from the outside. Specifically, the cover member 5 may make an end surface 3C of the sheet-like member 3 visible from the outside, as shown in Fig. 4. By making the end surface 3C of the sheet-like member 3 visible from the outside with the cover member 5 installed, it is possible to easily perform a visual inspection of whether the sheet-like member 3 is installed in the compartment penetration portion 15.

The cover member 5 is preferably installed so as to be in contact with the sheet-like member 3 and the insert 21. By installing the cover member 5 so as to be in contact with the sheet-like member 3 and the insert 21, the sheet-like member 3 and the cover member 5 can close the opening 13C of the partition section 11, thereby improving the fire resistance.

The cover member 5 is installed so as to form a gap 40 between the sheet-like member 3 and the cover member 5. The gap 40 between the sheet-like member 3 and the cover member 5 allows the cover member 5 to be fixed with a margin for the axial movement of the insert 21. The cover member 5 is fixed to the insert 21 with a margin, so that even if the insert 21 arranged inside the sheet-like member 3 and the cover member 5 is moved in the axial direction after the sheet-like member 3 and the cover member 5 are installed, the margin of the cover member 5 prevents the sheet-like member 3 and the cover member 5 from moving together with the insert 21. By preventing the sheet-like member 3 and the cover member 5 from moving together with the insert 21, it is possible to suppress the sheet-like member 3 and the cover member 5 from shifting from the partition penetration portion 15. In other words, with this configuration, the sheet-like member 3 and the cover member 5 can be maintained and arranged at an appropriate position in the partition penetration portion 15, and the fire resistance of the partition penetration portion 15 can be maintained.
There may be various configurations in which there is a gap 40 between the sheet-like member 3 and the cover member 5, and the cover member 5 is fixed with a margin for axial movement of the insert 21. For example, there may be a configuration in which at least a part of the cover member 5 is made of a material having flexibility or stretchability so that it can be bent or curved, and a configuration in which at least a part of the cover member 5 is fixed to the insert 21 with slack, etc.

The cover member 5 may be made of a single layer of a fire-resistant material, a single layer of a non-combustible material, or may have both a fire-resistant and a non-combustible material layer, but preferably has a non-combustible material layer, and more preferably is made of a non-combustible material layer. Also, the cover member 5 may have layers other than the fire-resistant and non-combustible material layers, such as a material layer made of a material other than a non-combustible material, an adhesive layer, etc.
The cover member 5 is preferably made of a metal foil such as aluminum foil, glass cloth, or a metal foil composite that is a composite of a metal foil and a glass cloth such as aluminum glass cloth. These constitute the non-combustible material layer. Among these, aluminum glass cloth is more preferable from the viewpoint of fire resistance.
The thickness of the noncombustible material layer is not particularly limited, but is, for example, 0.01 to 1 mm, and preferably 0.05 to 0.5 mm. When the noncombustible material layer has a thickness equal to or less than these upper limits, flexibility is imparted to the cover member 5. Therefore, even if the cover member 5 has a noncombustible material layer, it can be wrapped around the outer periphery of the insert 21 while being in close contact with the outer periphery. Furthermore, when the cover member has a thickness equal to or greater than the lower limit, fire resistance is easily ensured.

As described above, the cover member 5 is preferably a sheet that can be deformed to cover the sheet-like member 3, but it is preferable that the cover member 5 is thinner than the sheet-like member 3 so that it is flexible and can be easily deformed. The thickness of the cover member 5 is not particularly limited, but is, for example, 0.01 to 1 mm, and preferably 0.05 to 0.5 mm.

The fire-resistant material layer used in the cover member 5 is preferably a thermally expandable material that expands when heated. The thermally expandable material prevents the spread of fire by expanding in the event of a fire. The thermally expandable material is preferably formed from the above-mentioned thermally expandable resin composition. The fire-resistant material layer may also have adhesive properties.
The thickness of the fireproof layer is not particularly limited, but is, for example, 0.01 to 1 mm, preferably 0.05 to 0.5 mm. When the fireproof layer has a thickness equal to or less than these upper limits, flexibility is imparted to the cover member 5. Therefore, even if the cover member 5 has a fireproof layer, it can be wrapped around the outer periphery of the insert 21. Furthermore, when the cover member 5 has a thickness equal to or more than the lower limit, fire resistance is easily ensured.

The cover member 5 may have a fireproof material layer having adhesive properties or may have an adhesive layer. The fireproof material layer having adhesive properties and the adhesive layer may form the outermost surface of the cover member 5.
With the above-described configuration, the cover member 5 can be fixed to the sheet-like member 3 or the insert 21 without using a fixing member separate from the cover member 5. In addition, by imparting adhesiveness to the fireproof material layer itself, it is not necessary to provide an adhesive layer, and therefore the configuration of the cover member 5 can be further simplified.
When the cover member 5 has an adhesive fireproof material layer or an adhesive layer on its outermost surface, a release sheet may be attached to the outermost surface. The release sheet may be peeled off from the outermost surface when the cover member 5 is used.

The construction method of the partition penetration processing structure 10 includes a step of installing the above-mentioned sheet-like member 3 so as to block at least a part of the gap 13E between the opening 13C of the partition penetration portion 15 provided in the partition portion 11 and the insert 21. Then, the sheet-like member 3 is covered with the cover member 5 installed on the sheet-like member 3, and a part of the cover member 5 is fixed to the insert 21, thereby making the construction easy.

The sheet-like member 3 and cover member 5 used in the construction may be separate. If they are separate, the sheet-like member 3 is placed on the partition section 11, and then the cover member 5 is adhered to the sheet-like member 3 and installed, and the sheet-like member 3 is covered with the installed cover member 5. The sheet-like member 3 and cover member 5 used in the construction may be an integrated unit in which the sheet-like member 3 and cover member 5 are adhered in advance.

According to the configuration of the present embodiment, the gap 13E inside the opening 13C of the compartment penetration part 15 is blocked by the sheet-like member 3 and the cover member 5, and at least the sheet-like member 3 contains a fire-resistant material. Therefore, it is possible to impart appropriate fire resistance to the compartment penetration part treatment structure 10.
In addition, in this embodiment, a fireproof structure is formed by the sheet-like member 3 and the cover member 5 without placing filler materials such as fireproof putty or rock wool inside the compartment penetration portion 15, so there is no variation among workers.

Furthermore, in this embodiment, at least a portion of the sheet-like member 3 and the cover member 5 are exposed and visible from the outside. If a fixing member is provided to fix the sheet-like member 3 and the cover member 5, the fixing member should also be arranged in a position that is visible from the outside. No other members than the insert 21 are provided inside the partition penetration portion 15. Therefore, the partition penetration treatment material can be easily inspected visually or by photographing whether it has been installed as specified. Also, forgetting to install the material is less likely to occur.

The adhesive layer is preferably formed of an adhesive, and examples of the adhesive that can be used include acrylic adhesives, urethane adhesives, rubber adhesives, and silicone resin adhesives. The adhesive layer may be non-flammable, semi-non-flammable, or flame-retardant, and a flame retardant may be blended into the adhesive used. The thickness of the adhesive layer is, for example, 5 to 400 μm, and preferably 10 to 150 μm.
By configuring the cover member 5 to have an adhesive layer on one surface 5A, the cover member 5 can be fixed to the insertion body 21 without using a fixing member separate from the cover member 5.
When an adhesive layer is provided on one surface 5A of the cover member 5, a release sheet may be attached to the one surface 5A. The release sheet may be peeled off from the one surface 5A when the cover member 5 is used.

The cover member 5 is made of an elastic foam having flexibility capable of conforming to the outer periphery of the insert 21. Specific examples of the elastic foam include olefin-based resin foam and urethane-based resin foam.
The thickness of the elastic foam is not particularly limited, but is, for example, 0.1 to 10 mm, and preferably 0.15 to 5 mm. When the elastic foam has a thickness equal to or less than these upper limits, flexibility is imparted to the cover member 5. Therefore, the cover member 5 can be wrapped around the outer periphery of the insert 21 while being in close contact with the outer periphery. Furthermore, when the elastic foam has a thickness equal to or greater than the lower limit, the cover member 5 can be easily disposed.

According to the configuration of the present embodiment, the gap 13E inside the opening 13C of the compartment penetration part 15 is filled with the sheet-like member 3 and the cover member 5, and at least the sheet-like member 3 contains a fire-resistant material. Therefore, it is possible to impart appropriate fire resistance to the compartment penetration part treatment structure 10.
As described above, the compartment penetration processing structure 10 is constructed by preparing the sheet-like member 3 and the cover member 5, and first installing the sheet-like member 3 so as to close the gap 13E between the opening 13C of the compartment penetration part 15 and the insert 21. Next, the cover member 5 is wrapped around the insert 21 one or more times, and the cover member 5 is fixed so as to cover at least a part of the sheet-like member 3. Therefore, construction is easy.
In addition, in this embodiment, a fireproof structure is formed by the sheet-like member 3 and the cover member 5 without placing filler materials such as fireproof putty or rock wool inside the compartment penetration portion 15, so there is no variation among workers.

In the above description, the partition 11 is a hollow wall with a hollow space 13 inside, but it is not limited to a hollow wall and may be a wall without a hollow space, for example, made of a single wall material. Furthermore, the partition 11 is not limited to a wall of a building and may be a ceiling or floor of a building. Even if the partition is a ceiling or floor, it may have a structure with a hollow space between two partition materials, or a structure without a hollow space, for example, made of a single partition material.

The cover member 5 is not limited to the above embodiment. For example, in the compartment penetration processing structure 10 shown in Fig. 3, the cover member 5 is shown as four extension parts extending outward from the sheet-like member 3, but may be a single sheet-like member one size larger than the sheet-like member 3.
In addition, in the partition penetration processing structure 10 shown in FIG. 4, the cover member 5 is adhered to only a part of the surface 3A of the sheet-like member 3, but when using a single sheet-like cover member 5 that is one size larger than the sheet-like member 3, the cover member 5 can be adhered to the entire surface 3A of the sheet-like member 3. That is, the cover member 5 may have a structure in which the sheet-like member 3 is laminated on one surface of the cover member 5. In such a structure, it is preferable that the cover member 5 has a noncombustible material layer. The sheet-like member 3 and the cover member 5 are combined with a noncombustible material layer and a fire-resistant material layer, thereby improving fire resistance. In addition, an adhesive layer may be provided on the surface of the cover member 5 to which the sheet-like member 3 is adhered, and this adhesive layer makes it easy to adhere to the sheet-like member 3.
Furthermore, the sheet-like member 3 may have a structure in which the base material, which is one layer of the sheet-like member 3, extends outward beyond the other layers. With such a structure, the extended portion of the base material can be used as the cover member 5 as it is.
Further, in the compartment penetration structure 10 shown in FIG. 3 and FIG. 4, a form in which the sheet-like member 3 and the cover member 5 are provided is shown, but the cover member 5 may be omitted.
In addition, in the compartment penetration processing structure, the sheet-like member is arranged to cover the opening of the partition, but this is not limited to such an arrangement and may, for example, be bent into a sleeve shape and inserted into the compartment penetration portion 15 for use.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.
The components used in the examples and comparative examples are shown below.

(resin)
PVB (manufactured by Sekisui Chemical Co., Ltd., product name "BH-3", hydroxyl group content 35 mol%, acetalization degree 64 mol%, acetyl group content 1 mol%)
Polybutene (manufactured by ENEOS Corporation, product name "Nippon Oil Polybutene LV-100", number average molecular weight 500)
Chloroprene rubber (manufactured by Tosoh Corporation, product name "SKYPRENE B-12", Mooney viscosity at 100°C 35)
Natural rubber (manufactured by Soktec, product name "HA Latex", Mooney viscosity at 100°C: 121)
Butyl rubber (manufactured by JSR Corporation, product name "JSR BUTYL 365", Mooney viscosity at 125°C 33)
Styrene-butadiene rubber (manufactured by Asahi Kasei Corporation, product name "Tufden 2003", Mooney viscosity at 100°C 33)
Nitrile-butadiene rubber (manufactured by JSR Corporation, product name "N520", Mooney viscosity at 100°C: 51)
Ethylene propylene rubber (manufactured by Sumitomo Chemical Co., Ltd., product name "Esprene 532", Mooney viscosity at 100°C 110)
Chlorosulfonated polyethylene (manufactured by Tosoh Corporation, product name "TOSO-CSM (registered trademark) TS-430", Mooney viscosity at 100°C: 58)
Epichlorohydrin rubber (manufactured by Daiso Co., Ltd., product name "Epichromer H", Mooney viscosity at 100°C: 50)
Acrylic rubber (manufactured by Nippon Zeon Co., Ltd., product name "Nipol AR51", Mooney viscosity at 100°C: 55)
Polyphenylene oxide (manufactured by Asahi Kasei Corporation, product name "Xyron S202")
- Petroleum resin (manufactured by Idemitsu Kosan, product name "Imarve")

(Thermal Expandable Layered Inorganic Material)
・Thermal expansion graphite 1 (manufactured by ADT, product name “ADT-351”, thermal expansion start temperature: 180°C)
Thermally expandable graphite 2 (manufactured by Air Water Corporation, product name "SS-3N", thermal expansion starting temperature: 200°C)
Thermally expandable graphite 3 (manufactured by Fuji Graphite Industries, product name "EXP-50S 150", thermal expansion starting temperature: 150°C)

(Specific Additives)
<Flame retardants>
Aluminum phosphite (manufactured by Taihei Chemical Industry Co., Ltd., product name "APA100")
Ammonium polyphosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name "APP")
<Heat absorbing agent>
Aluminum hydroxide (manufactured by Nippon Light Metals Co., Ltd., product name "BF013", average particle size 1 μm, thermal decomposition starting temperature 200 ° C., endothermic heat amount 1000 J / g)
Magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., product name "Kisuma 10", average particle size 0.9 μm, thermal decomposition starting temperature 280 ° C., endothermic heat amount 1350 J / g)
<Lubricant>
- Butyl acrylate oligomer (manufactured by ADEKA Corporation, product name "ADEKA STAB FC-113")
- Mixture of monooctadecyl phosphate and dioctadecyl phosphate (manufactured by ADEKA Corporation, product name "ADEKA STAB AX-71")
<Inorganic filler>
Calcium carbonate (Shiraishi Calcium Co., Ltd., product name "BF300")
・Carbon black (manufactured by Mitsubishi Chemical Corporation, product name "Diablack H")

(Plasticizer)
Diisodecyl phthalate (Tokyo Chemical Industry Co., Ltd., product name "DIDP")
Adipic acid ether ester (manufactured by ADEKA, product name "RS-107")
・Polyetherester (manufactured by ADEKA, product name "RS-700")

The methods for measuring and evaluating each physical property are as follows.
(Thermal expansion starting temperature)
A 2 cm square piece of fireproof material was placed on a hot plate set at 300° C., and the temperature at which the thickness became twice the initial thickness was recorded as the thermal expansion starting temperature.

(Expansion ratio)
Test pieces (length 100 mm, width 100 mm, thickness 2.0 mm) of the fire-resistant materials made of the fire-resistant resin compositions obtained in each of the Examples and Comparative Examples were prepared, and the test pieces were fed into an electric furnace and heated at 300°C or 600°C for 30 minutes. The thicknesses of the test pieces were then measured, and the expansion ratio was calculated as (thickness of test piece after heating)/(thickness of test piece before heating).

(residual hardness)
The heated test piece was placed in a compression tester (Kato Tech Co., Ltd., "Finger Feeling Tester") and compressed with a 0.25 cm ² indenter at a speed of 0.1 cm/sec to measure the breaking stress.

(Residue retention rate)
The weight of the test piece after heating in which the expansion ratio was measured at 300°C and 600°C was measured. The test piece was heated in a horizontal furnace for 1 hour along the heating curve of ISO834. The weight of the test piece after heating was measured. The residual weight ratio (%) of the test piece after the heating test to that before the heating test was calculated and used as a measure of the durability of the residue.

(Fire resistance test)
An opening with a diameter of 160 mm was opened in a concrete frame, and a PVC100 VU pipe (outer diameter 114 mm, thickness 3.1 mm, JIS standard K6741) was passed through it and piped 300 mm below the floor and 500 mm above the floor. The fireproof material obtained in each example and comparative example was bent into a sleeve shape and installed in the opening. The position of the pipe was adjusted so that each clearance between the sleeve and the pipe was 10 mm or more, and the pipe was heated in a horizontal furnace for 2 hours along the heating curve of ISO834. If the temperature of the penetrating pipe 25 mm above the floor was less than the initial temperature + 180 ° C and no flame was generated through the penetration, it was evaluated as PASS, and if it was more than the initial temperature + 180 ° C or the pipe above the floor penetrated and flame was generated, it was evaluated as FAIL.

[Examples 1 to 6, Comparative Examples 1 to 4]
A fire-resistant resin composition was obtained by putting a resin, a thermally expandable layered inorganic material, a flame retardant, a heat absorbing agent, a lubricant, an inorganic filler, a plasticizer, and a petroleum resin into a roll and kneading them for 5 minutes at 130° C. in the composition shown in Table 1 below. The obtained fire-resistant resin composition was press-molded at 130° C. for 3 minutes to obtain a heat-expandable sheet having a thickness of 1.5 mm (1.3 mm in Example 23).
The evaluation results are shown in Table 1.

As shown in each of the above examples, the fire-resistant material using the fire-resistant resin composition of the present invention had a sufficient expansion ratio, and the residue hardness and residue maintenance rate were also good, so that no flame broke out through the fire resistance test.
On the other hand, the fire-resistant materials produced in the comparative examples had low residue hardness and residue maintenance rate, did not expand even at high temperatures, and in all cases, penetration occurred and flames broke out as a result of the fire resistance test.

REFERENCE SIGNS LIST 3 sheet-like member 5 cover member 10 compartment penetration processing structure 11 partition portion 12A, 12B wall material 13 hollow portion 13A, 13B through hole 13C, 13D opening 13E gap 15 compartment penetration portion 21 insert 22 string-like member 30A, ... 30Y, 30Z substrate 31A, ... 31Y, 31Z fireproof material layer 32 slit 33 adhesive layer 40 gap

Claims (9)

A fire-resistant laminate comprising a fire-resistant resin composition, a substrate and an adhesive layer integrated with the fire-resistant material, and used to provide a fire-resistant structure for a compartment penetration part of a building,
The fire-resistant resin composition contains a resin, a plasticizer, an additive, and a thermally expandable layered inorganic material, and is used in a fireproof structure of a building,
The resin includes chloroprene rubber ,
the plasticizer has an ester structure,
the additives include a flame retardant and an inorganic filler;
A fire-resistant laminate, wherein the flame retardant is a phosphorus atom-containing compound (excluding those in which the fire-resistant resin composition contains a foaming agent in an amount of 5 parts by mass or more per 100 parts by mass of a thermosetting elastomer in the fire-resistant resin composition) . 10. The fire resistant laminate of claim 1, wherein the additive further comprises a heat absorbing agent and/or a lubricant. The fire-resistant laminate according to claim 1 or 2 , wherein the content of the plasticizer is 0.5 to 100 parts by mass per 100 parts by mass of the resin. The fire-resistant laminate according to any one of claims 1 to 3 , wherein the content of the thermally expandable layered inorganic material is 10 to 50 parts by mass per 100 parts by mass of the fire-resistant resin composition. The fire-resistant laminate according to any one of claims 1 to 4, wherein the content of the flame retardant is 15 to 60 parts by mass per 100 parts by mass of the resin. The fire-resistant laminate according to any one of claims 1 to 5, wherein the content of the inorganic filler is 5 to 80 parts by mass per 100 parts by mass of the resin. The fire-resistant laminate according to any one of claims 1 to 6, wherein the ratio of the resin content to the powder content (resin/powder) is 0.2 to 3. The fire-resistant laminate according to any one of claims 1 to 7, wherein the thermally expandable layered inorganic material is thermally expandable graphite. A compartment penetration treatment material comprising the fire-resistant laminate according to any one of claims 1 to 8 .