JP6876646B2 - Refractory sheet and its winding body - Google Patents

Description

The present invention relates to a refractory sheet and a wound body thereof.

Conventionally, a refractory sheet containing a refractory material in a resin component has been used in order to impart fire resistance to a structure such as a house. For example, Patent Document 1 discloses a refractory sheet used for a refractory resin sash. Has been done.

Among such refractory sheets, long refractory sheets are required because of their ease of construction and parts processing. Generally, refractory sheets use inorganic fillers such as heat-expandable graphite. Since it is contained in a large amount, it is difficult to disperse the filler in the matrix resin. Therefore, when the refractory sheet is made long, the tension generated at the time of winding is applied unevenly to the sheet, and the performance difference is likely to occur due to the thickness variation, the winding shape is defective, and the rollability of the wound body is improved. Problems of inferior (breaking during unfolding, meandering during winding and winding misalignment), poor aesthetics (foreign matter or air bubbles caught in a refractory sheet shine), high heat shrinkage, and poor independence There is. There is no long fireproof sheet that solves these problems.

Japanese Patent No. 4691324

One object of the present invention is to provide a vinyl chloride-based refractory sheet and a wound body thereof, which are excellent in at least one of expandability and aesthetics.

The present invention is as follows.

Item 1. A wound body formed by winding a refractory sheet containing a polyvinyl chloride resin containing a plasticizer and having a total length of 2 m or more.

Item 2. Item 2. The wound body according to Item 1, wherein a laminated body of a plurality of refractory sheets having a thickness of 0.5 mm or more and a thickness variation of 0.1 mm or less is wound.

Item 3. Item 2. The wound body according to Item 1 or 2, wherein the surface of the refractory sheet is provided with irregularities.

Item 4. Item 2. The wound body according to any one of Items 1 to 3, wherein the refractory sheet has a heat shrinkage rate of 1% or less in both the MD direction and the TD direction.

Item 5. Item 2. The wound body according to any one of Items 1 to 4, wherein the surface of the refractory sheet is matted.

Item 6. The total length is 2 m or more, the coefficient of thermal expansion of the refractory sheet is 1% or less in both the MD direction and the TD direction, the thickness of each refractory sheet is 0.5 mm or more, and the thickness variation is 0.1 mm or less. A refractory sheet comprising a resin composition containing a heat-expandable graphite and at least one of a heat-expandable inorganic substance other than the heat-expandable graphite and an inorganic filler in a binder resin.

Item 7. The heat-expandable graphite, the phosphorus compound, the flame retardant, and the inorganic filler are further contained, and the total content of the heat-expandable graphite, the phosphorus compound, the flame retardant, and the inorganic filler is 40 to 80% by mass. Item 6. The fireproof sheet according to Item 6.

Item 8. A resin composition having a total length of 2 m or more and having irregularities on the surface of the sheet, the binder resin containing heat-expandable graphite and one of a heat-expandable inorganic substance other than the heat-expandable graphite and an inorganic filler. Fireproof sheet consisting of.

Item 9. Item 2. The fireproof sheet according to Item 8, wherein the height of the unevenness on the surface of the sheet is 300 μm or less.

Item 10. Item 8. The refractory sheet according to Item 8, which includes a laminate of a plurality of refractory sheets having a thickness of each refractory sheet of 0.5 mm or more and a thickness variation of 0.1 mm or less.

Item 11. Item 2. The refractory sheet according to any one of Items 8 to 10, wherein the refractory sheet has a heat shrinkage rate of 1% or less in both the MD direction and the TD direction.

Item 12. Item 6. The fireproof sheet according to any one of Items 6 to 11, wherein the surface of the fireproof sheet is matted.

Item 2. The refractory sheet according to any one of Items 6 to 12, wherein the temperature of the tan δ peak when the dynamic viscoelasticity is measured at a temperature dispersion (heating rate of 5 ° C./min) under 13.1 Hz is 80 ° C. or less. ..

Item 14. A wound body obtained by winding the refractory sheet according to any one of Items 6 to 13.

The refractory sheet of the present invention and its wound body are excellent in at least one of expandability and aesthetics. The refractory sheet and its wound body may also have excellent heat shrinkage and self-supporting properties.

The schematic perspective view of the winding body of 1st Embodiment of this invention. FIG. 3 is a schematic perspective view showing a state in which the wound body of FIG. 1 is extended to a sheet state. A schematic front view of a laminated body of a plurality of refractory sheets. A schematic perspective view of another example of a refractory sheet in which the surface of the refractory sheet is provided with irregularities by embossing. (A) A schematic perspective view of another example of a refractory sheet in which ribs are provided on the surface of the refractory sheet. (B)-(d) Schematic perspective view showing an example of another rib. A schematic perspective view of another example of a refractory sheet in which the surface of the refractory sheet is matted.

The first embodiment in which the present invention is embodied in a wound body and a refractory sheet will be described with reference to FIGS. 1 and 2.

The winding body 1 of the first embodiment of the present invention shown in FIG. 1 is formed by winding a refractory sheet 2 formed of a resin composition containing a polyvinyl chloride-based resin containing a plasticizer. As shown in FIG. 2, when the winding body 1 of FIG. 1 is extended so that the refractory sheet 2 becomes flat, X is the length of the refractory sheet 2, Y is the width of the refractory sheet 2, and Z is the refractory sheet. It is a thickness of 2. In the present invention, the total length X of the fireproof sheet 2 is 2 m or more, the upper limit value is preferably 1000 m or less, and the total length X is more preferably 200 m or more. The width Y of the refractory sheet 2 is not particularly limited, but is preferably 0.5 m or more and 5 m or less. The thickness Z of the refractory sheet 2 is not particularly limited, but preferably the lower limit is 0.5 mm and the upper limit is 100 mm or less. More preferably, the thickness Z is 1 mm or more and 5 mm or less. By increasing the thickness Z, the refractory sheet 2 can be lengthened. The thickness variation is preferably 0.1 mm or less (that is, ± 0.1 mm or less). It is more preferable that the thickness Z is 0.5 mm or more and the thickness variation is 0.1 mm or less, and it is further preferable that the thickness Z is 0.5 mm to 5 mm and the thickness variation is 0.1 mm or less. .. By setting the thickness Z to 0.5 mm or more and the thickness variation to 0.1 mm or less, air bubbles and fogging on the surface of the refractory sheet 2 can be suppressed, and the deployability of the refractory sheet 2 is also improved.

The form of the winding body 1 is not particularly limited, but the refractory sheet 2 may be wound around a bobbin (not shown) to form the winding body 1, and the fireproof sheet 2 may be wound around the winding core to record. The winding body 1 may be wound in a winding shape.

In order to increase the accuracy of the thickness sheet, it is necessary to efficiently disperse the inorganic filler in the resin component constituting the refractory sheet 2.

In order to improve the dispersibility of the inorganic filler, for example, as will be described later, a method of controlling the particle size of the inorganic filler can be exemplified. Further, as one of the preferred embodiments of the present invention, a method of controlling the particle size ratio between the particle size of the heat-expandable inorganic substance and the particle size of the inorganic filler can be exemplified. The preferred range of the particle size ratio of the particle size of the heat-expandable inorganic substance to the particle size of the inorganic filler (particle size of the heat-expandable inorganic substance / particle size of the inorganic substance) is 1 to 1000, and a more preferable range is 3 to 500. Yes, a more preferred range is 5-50. By setting such a numerical range, kneading can be performed efficiently in a short time.

“MD” refers to the flow direction (MD direction) of the resin composition at the time of molding the fireproof sheet 2, and “TD” refers to the direction perpendicular to the flow direction of the resin composition (TD direction). The heat shrinkage rate of the refractory sheet 2 of the present invention is preferably 1% or less in both the MD direction and the TD direction. The heat shrinkage of the refractory sheet 2 can be improved by annealing at the time of manufacturing the resin composition. For example, annealing the resin composition at a temperature of 120 ° C. for about 3 minutes to 1 hour, more preferably about 30 minutes to 1 hour. Therefore, the heat shrinkage rate of the refractory sheet 2 can be reduced.

Other methods for reducing the coefficient of thermal expansion of the refractory sheet 2 can be realized by those skilled in the art by appropriately selecting the amounts of the heat-expandable inorganic substance, the inorganic filler, and the plasticizer with respect to the resin component. From the viewpoint of reducing the stress strain relaxation component and increasing the elastic component, the total amount of the thermally expandable inorganic substance and the inorganic filler is added to the resin component (if the plasticizer is contained in the resin composition, the plasticizer is also included). On the other hand, it is preferably equal to or more than the same amount. Further, from the viewpoint of reducing the relaxation component, the resin component is preferably 35% by mass or less of the resin composition, and the polyvinyl chloride resin is more preferably 35% by mass or less of the resin composition.

Further, preferably, the refractory sheet 2 of the present invention has a temperature (also referred to as "tan δ peak temperature") of 80 ° C., which indicates the maximum value of tan δ when dynamic viscoelasticity is measured under the conditions of a frequency of 1 Hz and a strain of 1%. It is as follows. Preferably, the tan δ peak temperature is -30 to 60 ° C.

According to this configuration, breakage or the like is less likely to occur during winding, and winding is possible even if the diameter of the winding core is small, so that the winding length can be increased, which is beneficial.

In the present invention, tan δ can be measured by the following method. The dynamic viscoelasticity of the fireproof sheet is measured by a viscoelasticity measuring device (for example, "ARES" manufactured by Leometrics) by a shearing method under the conditions of a strain amount of 1.0% and a frequency of 1 Hz. Tan δ can be measured by measuring the temperature dispersion of dynamic viscoelasticity at 5 ° C./min. The tan δ peak temperature means a temperature indicating the maximum value of the obtained tangent loss.

The tan δ peak temperature can be controlled by selecting the type of resin component in the resin composition constituting the refractory sheet 2 and the selection of a liquid additive such as a plasticizer. In the system of the resin composition containing a large amount of heat-expandable graphite and the inorganic filler, the resin component is preferably a polyvinyl chloride-based resin from the viewpoint of the range of selection of liquid additives such as plasticizers. Further, from the viewpoint of resin structure control, the resin component is preferably EVA resin or epoxy resin, which will be described later. These resins can easily control the tan δ peak temperature while maintaining the kneadability.

In addition, in FIGS. 1 and 2, the refractory sheet 2 is obtained by extending the winding body 1, but the winding body 1 is cut in the longitudinal direction and / or the width direction to become a part of the winding body 1. Is also included in the fireproof sheet 2.

The refractory resin material constituting the refractory sheet 2 will be described in detail below.

The refractory resin material constituting the refractory sheet 2 is a resin composition containing a binder resin as a resin component, a heat-expandable inorganic substance, an inorganic filler, and a plasticizer.

The resin component includes a polyvinyl chloride resin. Examples of the polyvinyl chloride-based resin include a polyvinyl chloride homopolymer; a copolymer of a vinyl chloride monomer and a monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer; (co) other than vinyl chloride. Examples thereof include a graft copolymer obtained by graft-copolymerizing vinyl chloride as a polymer, and these may be used alone or in combination of two or more.

In the present invention, the chlorinated polyvinyl chloride resin, which is a chlorinated product of the polyvinyl chloride resin, is also included in the polyvinyl chloride resin.

The average degree of polymerization of the polyvinyl chloride resin is not particularly limited, but when it becomes small, the physical properties of the molded product deteriorate, and when it becomes large, the melt viscosity becomes high and molding becomes difficult. Therefore, 600 to 1500 is used. preferable.

The heat-expandable inorganic substance expands when heated, and the heat-expandable inorganic substance is not particularly limited, and examples thereof include vermiculite, kaolin, mica, heat-expandable graphite, a metal phosphate salt, and a silas balloon. it can. Thermally expandable graphite is a conventionally known substance, which is obtained by treating powders such as natural scaly graphite, pyrolytic graphite, and kiss graphite with an inorganic acid and a strong oxidizing agent to form a graphite intercalation compound. Yes, it is a kind of crystalline compound that maintains the layered structure of carbon. Examples of the inorganic acid include concentrated sulfuric acid, nitric acid and selenic acid. Examples of the strong oxidizing agent include concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, dichromate, hydrogen peroxide and the like.

Shirasu (white sand, white state) refers to inorganic volcanic ejecta containing pumice or volcanic ash. Shirasu also includes refined and processed natural shirasu. Preferably, unfired shirasu is used as the shirasu. The average particle size of Shirasu is preferably 2 to 1000 μm. The foaming start temperature of Shirasu is not limited, but is usually 800 ° C. or higher.

The heat-expandable graphite obtained by the acid treatment as described above may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like. The particle size of the heat-expandable graphite is preferably 20 to 200 mesh. If the particle size is 200 mesh or smaller, the degree of expansion of graphite is sufficient for the expanded heat insulating layer to be obtained, and if the particle size is 20 mesh or larger, the dispersibility when blended in the resin is good and the physical properties are poor. It is good. Examples of commercially available products of heat-expandable graphite include "GREP-EG" manufactured by Tosoh Corporation and "GRAFGUARD" manufactured by GRAFTECH.

The heat-expandable graphite used in the present invention preferably has an average aspect ratio of 20 or more, more preferably 25 or more, but if it is too high, cracks may occur, so 1000 or less is used. preferable. When the average aspect ratio of the heat-expandable graphite is 20 or more, it contributes to the high expandability of the resin composition and the high residual hardness after combustion.

The aspect ratio is the value obtained by dividing the maximum dimension (major diameter) of the heat-expandable graphite piece by the minimum dimension (minor diameter). Then, the aspect ratio is measured for 10 or more heat-expandable graphite pieces, and the average value is taken as the average aspect ratio. The major axis and minor axis of the heat-expandable graphite can be measured using, for example, a field emission scanning electron microscope (FE-SEM).

When the expanded heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and also acts as an aggregate to improve the strength of the expanded heat insulating layer. The inorganic filler is not particularly limited, and for example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; calcium hydroxide, magnesium hydroxide. Water-containing inorganic substances such as aluminum hydroxide and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate and barium carbonate can be mentioned.

In addition to these, as inorganic fillers, calcium salts such as calcium sulfate, gypsum fiber, and calcium silicate; silica, diatomaceous soil, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, active white clay, and sepiolite. , Imogolite, serisite, glass fiber, glass beads, silica-based balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate " MOS ”(trade name), lead zirconate titanate, zinc stearate, calcium stearate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fibers, fly ash, dehydrated sludge, etc. Can be mentioned. These inorganic fillers may be used alone or in combination of two or more.

The particle size of the inorganic filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance, so that the inorganic filler has a small particle size, but when it is 0.5 μm or more, the dispersibility is good. When the amount added is large, the viscosity of the resin composition increases and the moldability decreases as the high filling progresses, but the viscosity of the resin composition can be decreased by increasing the particle size. A large diameter is preferable, but a particle size of 100 μm or less is desirable from the viewpoint of the surface properties of the molded product and the mechanical properties of the resin composition.

Examples of the inorganic filler include "Heidilite H-31" (manufactured by Showa Denko Co., Ltd.) having a particle size of 18 μm for aluminum hydroxide, "B325" (manufactured by ALCOA) having a particle size of 25 μm, and calcium carbonate having a particle size. Examples thereof include 1.8 μm “Whiten SB Red” (manufactured by Bikita Powder Industry Co., Ltd.) and “BF300” (manufactured by Bikita Powder Industry Co., Ltd.) having a particle size of 8 μm.

The resin composition preferably contains the heat-expandable inorganic substance in the range of 10 to 350 parts by mass and the inorganic filler in the range of 30 to 400 parts by mass with respect to 100 parts by mass of the resin component.

The total amount of the heat-expandable inorganic substance and the inorganic filler is preferably in the range of 50 to 600 parts by mass with respect to 100 parts by mass of the resin component.

When the total amount of the heat-expandable inorganic substance and the inorganic filler in the resin composition is 50 parts by mass or more, sufficient fire resistance is obtained by satisfying the residual amount after combustion, and when it is 600 parts by mass or less, the mechanical properties are mechanical. Is maintained.

Such a resin composition expands by heating to form a refractory heat insulating layer. According to this composition, the heat-expandable refractory material expands by heating such as a fire to obtain a required coefficient of thermal expansion, and after expansion, a residue having a predetermined heat insulating performance and a predetermined strength is formed. It is also possible to achieve stable fire protection performance.

Examples of the plasticizer include phthalate-based plasticizers such as di-2-ethylhexylphthalate (DOP), dibutylphthalate (DBP), diheptylphthalate (DHP), and diisodecylphthalate (DIDP); di-2-ethylhexyl adipate. Fatty acid ester plasticizers such as (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA); epoxidized ester plasticizers such as epoxidized soybean oil; polyester plasticizers such as adipic acid ester and adipate polyester; Trimeritic acid ester plasticizers such as tri-2-ethylhexyl trimerite (TOTM) and triisononyl trimerite (TINTM); orthophosphoric acid ester plasticizers such as trimethylphosphate (TMP) and triethylphosphate (TEP). And so on. These may be used alone or in combination of two or more.

The amount of the plasticizer used is preferably 20 to 200 parts by mass, and more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the resin component. When the amount of the plasticizer used is 20 parts by mass or more, sufficient impact resistance is obtained, and when it is 200 parts by mass or less, flame retardancy is exhibited. In addition, when heat-expandable graphite or inorganic filler is contained, the amount of plasticizer used is a resin component because the sheet may become hard and slit processing may become difficult when the refractory sheet is lengthened depending on the processing conditions. It is preferably 80 parts by mass or more with respect to 100 parts by mass. When slitting, it is preferable to heat the refractory sheet to, for example, 50 ° C. or higher, preferably 70 ° C. or higher in order to facilitate slitting.

Further, the resin composition constituting the heat-expandable refractory material may further contain a phosphorus compound in addition to the above-mentioned components in order to increase the strength of the expansion heat insulating layer and improve the fire protection performance. The phosphorus compound is not particularly limited, and is, for example, red phosphorus; various phosphate esters; metal phosphate salts; ammonium polyphosphates; melamine polyphosphate, melam polyphosphate, melem polyphosphate; lower phosphate; and the following chemical formula. Examples thereof include the compound represented by (1). Of these, red phosphorus, ammonium polyphosphate, and the compound represented by the following chemical formula (1) are preferable from the viewpoint of fire protection performance, and ammonium polyphosphate is more preferable from the viewpoint of performance, safety, cost, and the like. ..

In the chemical formula (1), R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms, which are the same or different. R2 is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or a carbon number of carbon atoms. It shows 6 to 16 aryloxy groups.

As the red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of moisture resistance and safety such as not spontaneously igniting during kneading, those in which the surface of the red phosphorus particles is coated with a resin are preferably used.

Examples of the phosphoric acid ester include phosphoric acid aryl esters such as triphenyl phosphate, tricredyl phosphate (TCP), trixylenyl phosphate, cresyldiphenyl phosphate, and xylenyl diphenyl phosphate; alkyl phosphates; bisphenol Abis, Examples thereof include bisphenol-based aromatic condensed phosphoric acid esters such as resorcinol bisdiphenyl phosphate, resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, and the like. However, those that are the above plasticizers are excluded. A preferred phosphate ester is tricresyl phosphate (TCP).

Examples of the metal phosphate salt include sodium phosphate, potassium phosphate, magnesium phosphate and the like.

Ammonium polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate and melamine-modified ammonium polyphosphate. Ammonium polyphosphate is preferably used from the viewpoint of handleability and the like. Examples of commercially available products include "AP422" and "AP462" manufactured by Clariant AG, "FR CROS 484" and "FR CROS 487" manufactured by Budenheim Ibica. The compound represented by the chemical formula (1) is not particularly limited, and for example, methylphosphonate, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonic acid, 2-methylpropylphosphonate, t- Butylphosphonic acid, 2,3-dimethyl-butylphosphonate, octylphosphonate, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphonate, methylethylphosphonate, methylpropylphosphinic acid, diethylphosphonate, dioctylphosphonate, phenylphosphine Acids, diethylphenylphosphonates, diphenylphosphonates, bis (4-methoxyphenyl) phosphonates and the like can be mentioned. Among them, t-butylphosphonic acid is preferable in terms of high flame retardancy, although it is expensive. The above phosphorus compounds may be used alone or in combination of two or more.

From the viewpoint of improving flame retardancy, a lower phosphate as a flame retardant is preferable as the phosphorus compound. "Lower phosphoric acid" refers to an inorganic phosphate that is not condensed, that is, is not polymerized among inorganic phosphates, and the phosphoric acids are primary phosphoric acid, secondary phosphoric acid, and tertiary phosphorus. Acids, metaphosphoric acid, phosphoric acid, hypophosphoric acid and the like can be mentioned. As salts, alkali metal salts (lithium salt, sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, calcium salt, strontium salt, barium salt), periodic table 3B metal salt (aluminum salt, etc.) , Transition metal salts (titanium salt, manganese salt, iron salt, nickel salt, copper salt, zinc salt, vanadium salt, chromium salt, molybdenum salt, tungsten salt), ammonium salt, amine salt, for example, guanidine salt or triazine salt (For example, melamine salt, melem salt, etc.) and the like, preferably a metal salt.

In one embodiment, the lower phosphate is at least one of a metal phosphate and a metal phosphite. The metal phosphite salt may be effervescent (thermally expandable). Further, the phosphorous acid metal salt may be used after being surface-treated with a surface treatment agent or the like in order to improve the adhesion with the matrix resin. As such a surface treatment agent, a functional compound (for example, an epoxy compound, a silane compound, a titanate compound, etc.) can be used.

Examples of such metal salts of lower phosphoric acid are aluminum primary phosphate, sodium primary phosphate, potassium primary phosphate, calcium primary phosphate, zinc primary phosphate, aluminum secondary phosphate, phosphorus secondary. Sodium phosphate, potassium dibasic phosphate, calcium dibasic phosphate, zinc dibasic phosphate, aluminum tertiary phosphate, sodium tertiary phosphate, potassium tertiary phosphate, calcium tertiary phosphate, zinc tertiary phosphate, phosphite Aluminum, sodium phosphite, potassium phosphite, calcium phosphite, zinc phosphite, aluminum hypophosphite, sodium hypophosphate, potassium hypophosphite, calcium hypophosphite, zinc hypophosphate, metaphosphoric acid Examples thereof include aluminum, sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, zinc metaphosphate and the like.

From the viewpoint of generating flammable gas such as phosphine gas, an aluminum salt is preferably used.

When a phosphorus compound is used, for example, the phosphorus compound is contained so that the total amount of the phosphorus compound and the heat-expandable inorganic substance is 20 to 400 parts by mass with respect to 100 parts by mass of the resin component. The amount of the phosphorus compound with respect to 100 parts by mass of the resin component is, for example, 20 parts by mass or more and 200 parts by mass or less.

When the phosphorus compound is contained, the content thereof is not particularly limited, but the total content of the phosphorus compound, the flame retardant, the inorganic filler and the heat-expandable graphite is 40 to 80% by mass, preferably 50 to 70. It is said to be% by mass. According to such a configuration, the fire resistance performance of the fire resistance sheet is enhanced.

Further, in the present invention, it is preferable to use a heat-expandable inorganic substance other than the heat-expandable graphite in combination with the heat-expandable graphite. When used in combination, expansion can be continued over a wide temperature range and for a long time, and stable fire resistance can be exhibited. The heat-expandable inorganic substance is not particularly limited, and examples thereof include heat-expandable inorganic substances other than the above-mentioned heat-expandable graphite, particularly phosphorous acid metal salt, silas balloon, and the like. When the heat-expandable inorganic substance is used in combination, the content thereof is not particularly limited, but 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, more preferably the heat-expandable inorganic substance with respect to 100 parts by mass of the heat-expandable graphite. Is 30 parts by mass to 200 parts by mass.

Further, the resin compositions used in the present invention are, if necessary, phenol-based, amine-based, sulfur-based and other antioxidants, metal damage inhibitors, and antistatic agents, as long as they do not impair the object of the present invention. , Stabilizers, cross-linking agents, lubricants, softeners, pigments, antistatic resins, additives such as molding aids, and antistatic agents such as polybutene and petroleum resins.

The resin composition is not particularly limited as long as it is insulated by the expansion layer when exposed to a high temperature such as in a fire and has the strength of the expansion layer, but under a heating condition of ^{50 kW / m 2.} It is preferable that the volume expansion rate after heating for 30 minutes is 3 to 50 times. When the volume expansion coefficient is 3 times or more, the expansion volume can sufficiently fill the burned portion of the resin component, and when the expansion volume is 50 times or less, the strength of the expansion layer is maintained and the penetration of flame is prevented. The effect is maintained.

Each component of the resin composition is kneaded using a known device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a Raikai machine, and a planetary stirrer, and molded by a known molding method. Thereby, the fireproof sheet 2 can be obtained as the winding body 1.

For example, the mixture kneaded with a kneader mixer is molded on a sheet with an inverted L-shaped calendar, cooled once with a cooling roll, blown with hot air at a high temperature (for example, 120 ° C.) in an annealing furnace, and then passed through the cooling roll again. By winding with a winding roll, the refractory sheet 2 can be obtained as the winding body 1.

An adhesive layer may be formed on the surface of the refractory sheet 2. The method of applying the adhesive layer to the surface of the fireproof sheet 2 is not particularly limited, but a method of applying an adhesive to the release paper and transferring it to the fireproof sheet 2, a silicone release agent or the like is applied to one side of the fireproof sheet 2. Examples thereof include a method of applying an adhesive to a surface that has not been released from the mold after being subjected to a mold release treatment such as coating, or a method of attaching a double-sided tape to the fireproof sheet 2.

The refractory sheet 2 can be used to impart fire resistance to structures such as windows, shoji screens, doors (ie, doors), bran, and fittings such as balustrades; ships; vehicles; and elevators. In particular, it is used for sealing openings or gaps in these structures and for fire protection. For example, the refractory sheet 2 can be used as an airtight material such as a tight material or a sealing material for improving the airtightness or watertightness of fittings. The structure may be made of any material such as metal, synthetic resin, wood, or a combination thereof. The "opening" refers to an opening existing between a structure and another structure or in the structure, and the "gap" refers to an opening formed between two facing members or portions in the opening.

Although the present invention has been described above with respect to the wound body 1 and the refractory sheet 2 of the first embodiment, the present invention is not limited to this, and various modifications such as the following are possible.

The resin component of the resin composition constituting the fireproof sheet 2 is not limited to the polyvinyl chloride resin, and may be another thermoplastic resin, a thermosetting resin, a rubber substance, or a combination thereof. When a resin component other than the polyvinyl chloride resin is used, the plasticizer may not be contained. The other components may be the same as those described for the resin composition constituting the refractory sheet 2 of the first embodiment.

Examples of the thermoplastic resin include polyolefin resins such as polypropylene resins, polyethylene resins, poly (1-) butene resins, and polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, and polycarbonates. Synthesis of elastomers such as based resins, polyphenylene ether resins, (meth) acrylic resins, polyamide resins, phenol resins, polyurethane resins, polyisobutylene, ethylene-vinyl acetate (EVA), olefin elastomers (TPO), etc. Examples include resins.

Examples of the thermosetting resin include polyurethane, polyisocyanate, polyisocyanurate, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide.

Rubber substances include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber. , Epichlorohydrin rubber, polyvulverable rubber, non-vulture rubber, silicon rubber, fluororubber, urethane rubber and other rubber substances.

As these synthetic resins and / or rubber substances, one kind or two or more kinds can be used.

Among these synthetic resins and / or rubber substances, those having soft and rubber-like properties are preferable. Those having such properties can be highly filled with an inorganic filler, and the obtained resin composition becomes flexible and easy to handle. In order to obtain a more flexible and easy-to-handle resin composition, a non-vulcanized rubber such as butyl or a polyethylene-based resin is preferably used. Instead, an epoxy resin is preferable from the viewpoint of increasing the flame retardancy of the resin itself and improving the fire protection performance.

The resin composition constituting the refractory sheet 2 does not have to contain both the heat-expandable inorganic substance and the inorganic filler, and may contain either the heat-expandable inorganic substance or the inorganic filler.

As shown in FIG. 3, the refractory sheet may be a refractory sheet 3 made of a laminated body in which a plurality of refractory sheets 2 are laminated. Lamination may be performed by laminating a plurality of refractory sheets 2 with an adhesive means such as an adhesive, or by thermocompression bonding. Also in this case, the thickness of the refractory sheet 3 is preferably 1 mm or more, and the thickness variation is 0.1 mm or less, so that a refractory sheet having excellent independence can be obtained.

As shown in FIGS. 4 and 5 (a) to 5 (d), unevenness may be provided on at least one surface of the refractory sheet 2. In FIG. 4, embossed unevenness 4 is provided on at least one surface of the refractory sheet 2. In this figure, the concave portion 4a and the portion 4b of the fireproof sheet 2 protruding from the concave portion 4a around the concave portion 4a form the unevenness 4, but instead, the convex portion of the fireproof sheet 2 and the convex portion of the convex portion. The portion of the refractory sheet 2 that is dented with respect to the surrounding convex portion may form the unevenness 4. The unevenness 4 can be formed by molding the refractory resin composition constituting the refractory sheet 2 with an embossed roll at the time of manufacturing the refractory sheet 2. The embossed unevenness 4 is preferably formed in an area occupying at least 30% or more of one surface of the refractory sheet 2, more preferably formed in an area occupying 50% or more, and at least in the refractory sheet 2. It is more preferable that it is formed on the entire surface. By providing the unevenness 4 on at least one surface of the refractory sheet 2, the self-supporting property of the refractory sheet 2 is improved even if the thickness variation of the refractory sheet 2 is larger than 0.1 mm. Further, if the unevenness 4 is provided on at least one surface of the refractory sheet 2, the contact area between the refractory sheet portion newly laminated from above and the lower refractory sheet portion decreases when the refractory sheet 2 is wound. Therefore, it is possible to reduce the stress in the tangential direction of the lower refractory sheet portion due to the refractory sheet portion newly laminated from above. Therefore, the winding tightening can be suppressed, blocking (a phenomenon in which the refractory sheet cannot be unwound) is prevented, and the deployability of the refractory sheet 2 is also improved. As a result of being able to absorb the winding tightness, fogging on the surface of the refractory sheet 2 is also prevented.

The shape of the embossed embossed is not particularly limited, but the height of the embossed unevenness is preferably 300 μm or less. If it is 300 μm or more, when the sheet surface is subjected to a force in the shearing direction during winding or handling, the embossed portion is broken due to the refractory sheet containing a large amount of filler, and the appearance of the sheet surface is impaired. In some cases. From this point of view, the uneven height is more preferably 50 μm or less. The embossed shape is also not particularly limited, and for example, a linear shape, a staggered square shape, a hexagonal shape, a round shape, a spherical shape, etc. are preferably used for this purpose, but the shape and arrangement pattern are based on the viewpoint of the contact area. The embossing area (area of the recess 4a) is preferably 25% or more. Further, the refractory sheet contains heat-expandable graphite having a large particle size in order to develop fire resistance. The heat-expandable graphite has a particle size distribution, but if a portion having a coarse particle size is present on the sheet surface in a state of being oriented in the flow direction of the sheet, the graphite may reflect light and impair the appearance of the surface. This defect can be improved by embossing the heat-expandable graphite so as not to orient it. Specifically, embossing is applied so that the dimensions of the heat-expandable graphite are equal to or less than the length of the long side direction, and the dimensions of the convex portion of the sheet are set to be less than or equal to the length of the heat-expandable graphite. Is preferable. Specifically, considering the long side diameter of the heat-expandable graphite, it is preferable to set the embossing shape and the interval so as to be 2500 μm or less, preferably 1500 μm or less, and more preferably 1000 μm or less.

In FIGS. 5A to 5D, ribs 5 as irregularities are provided on at least one surface of the refractory sheet 2. The rib 5 and at least one surface portion of the refractory sheet 2 adjacent to the rib 5 form an unevenness. In FIG. 5A, the rib 5 is composed of a plurality of ribs 5a extending in the MD direction (longitudinal direction in the figure) of the refractory sheet 2 and a plurality of ribs 5b extending in the TD direction (width direction in the figure) of the refractory sheet 2. Has been done. However, as shown in FIG. 5B, the refractory sheet 2 may be composed of only a plurality of ribs 5a extending in the MD direction (longitudinal direction in the drawing). As shown in FIG. 5C, only a plurality of ribs 5b extending in the TD direction (width direction in the drawing) of the refractory sheet 2 may be configured. As shown in FIG. 5D, the refractory sheet 2 may be composed of a plurality of ribs 5c extending obliquely with respect to the MD direction (longitudinal direction in the drawing).

The rib 5 is composed of, for example, a polyvinyl chloride resin, but is not limited to this, and may be composed of another thermoplastic resin, a thermosetting resin, or a rubber substance. The rib 5 may be formed at the time of molding the refractory sheet 2, or may be formed at a different timing, for example, at a work site after the refractory sheet 2 is manufactured.

By providing such a rib 5, the independence of the refractory sheet 2 is reinforced, the bending of the refractory sheet 2 is prevented, and the installation of the refractory sheet 2 on the structure becomes easy. Further, if the ribs are provided, when the refractory sheet 2 is wound, the stress in the tangential direction of the lower refractory sheet portion due to the refractory sheet portion newly laminated from above can be reduced, so that the winding is tightened. It can be suppressed, and the expandability of the refractory sheet 2 is also improved. As a result of being able to absorb the winding tightness, fogging and blocking of the surface of the refractory sheet 2 are also prevented.

As shown in FIG. 6, at least one surface of the refractory sheet 2 may be a matted surface 6. The matte surface 6 is formed by finely concavo-convex processing the surface of the refractory sheet 2 by surface processing with an embossed roll or the like. For example, the ten-point average roughness Rz on the matte surface 6 is 10 μm or more and 40 μm or less. By applying such a matte surface 6, glare on the surface of the refractory sheet 2 can be reduced, and light due to foreign matter or air bubbles caught in the refractory sheet can be diffused.

This matte processing can also be applied to the surface of the refractory sheet 2 provided with the embossed unevenness 4 of FIG. 4 and the surface of the refractory sheet 2 provided with the rib 5 as shown in FIG.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

1. 1. Production of refractory sheet Each component shown in Tables 1 to 3 was mixed with a kneading kneader. The kneading temperature was 150 ° C. and the kneading time was 7 minutes and 30 seconds, and the refractory resin compositions of Test Examples 1 to 3 were produced.

From the refractory resin compositions of Test Examples 1 to 3 obtained above, the refractory of Examples 1 to 6, 8 and 9 in Table 5 and Comparative Examples 1 to 2 having a width of 1000 mm and a thickness of 1.5 mm by calendar molding. The sheet was manufactured.

The refractory sheets of Examples 5 to 8 were calendar-molded into a refractory sheet having a width of 1000 mm, a thickness of 1.5 mm, and a winding length of 400 m.

The rib was formed on the surface of a refractory sheet by using an embossed roll for one of the calendar rolls and molding a refractory resin composition with the embossed roll, and then winding the rib to obtain a long refractory sheet. (See Table 5 for Examples 3 to 6 and winding length).

In the case of annealing, the long sheet was re-expanded, and by adjusting the feeding speed, it was passed through a heating furnace at an arbitrary temperature and heating time, and rewound to obtain an annealed long sheet ( Examples 1, 2, 4, 8, 9, Comparative Example 1).

The refractory sheets of Examples 1 to 4 and Comparative Examples 1 and 2 are all formed from a refractory resin composition containing a polyvinyl chloride resin having the same composition of Test Example 1.

The heat shrinkage of each refractory sheet in the MD direction and the TD direction was controlled by changing the take-up tension when the refractory resin composition of Test Example 1 was formed into a refractory sheet and changing the annealing conditions.

Each component shown in Table 4 was kneaded with a static mixer at 25 ° C. for 5 minutes. The obtained paste-like kneaded product was sandwiched between two polyethylene terephthalate films and continuously passed through the gaps of the nip rolls to form a sheet. The gap between the nip rolls was passed through the thickness gap of the obtained sheet molded product, and then passed through a heating furnace at 135 ° C. for 45 minutes to be effective, and then wound up to obtain a refractory long sheet of Example 7 ( See Table 5 for the winding length).

2. Evaluation of the performance of the refractory sheet The thickness variation, independence, heat shrinkage rate, aesthetics and expandability of Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated according to the following criteria. The results are shown in Table 2.

[Thickness variation]
The thickness is measured at 5 points at equal intervals in the width direction of the refractory sheet, and in the length direction, the thickness is measured at each midpoint of each of the 9 equal parts of the winding length (each center of each section). Was measured, and a total of 50 points of thickness variation were evaluated.

[Evaluation of independence]
The obtained fireproof sheet was attached to a pellicle film made of aluminum alloy A7075 having an external dimension of 100 mm × 100 mm and a frame width of 2 mm with an acrylic adhesive. The state of the pellicle film at this time was visually evaluated.

-No tears, wrinkles or sagging on the pellicle membrane: ○
・ The pellicle film was torn, wrinkled or sagging: ×
The sample was sampled at equal intervals of 3 points in the width direction at each midpoint (each center of each section) of each line segment divided into 4 equal parts of winding length in the length direction, and evaluation was performed at a total of 15 points. The average value was adopted.

[Tanδ peak temperature]
The dynamic viscoelasticity of the obtained fireproof sheet is raised by a shearing method using a viscoelasticity measuring device (“ARES” manufactured by Leometrics) under the conditions of a strain amount of 1.0% and a frequency of 1 Hz. The temperature dispersion of dynamic viscoelasticity was measured at a speed of 5 ° C./min.
[Heat shrinkage rate]
According to JIS K 7133, the dimensions of the refractory sheet before and after heating were measured in the MD direction and the TD direction. The heating conditions were 70 ° C. for 22 hours.

For the sample, the winding length was sampled every 4 equal parts at 3 points in the width direction at equal intervals, and evaluation was performed at a total of 15 points, and the average value was adopted.

[Surface appearance]
After producing the obtained long refractory sheet, the refractory sheet cured at 40 ° C. for 1 week was evaluated by re-developing. In the process of unfolding, the appearance of the sheet was observed to determine whether or not air bubbles were observed on the surface, and the case where air bubbles of 5 mm or more in the width direction were not observed was evaluated as ◯, and the case where air bubbles were observed was evaluated as x.

Also, observe the presence or absence of surface fogging (surface peeling when the blocking is peeled off), and ^{if peeling of an area of 25 cm 2} or more is observed, x, if it is observed but ^{less than 25 cm 2} , △, not observed. The case was marked as ○.
[Expandability (unrollability)]
The expandability of the fireproof sheet was evaluated as follows.
・ The fireproof sheet can be unfolded by rotating the roll in the unwinding direction: 〇 ・ The sheet does not unfold even if the roll is rotated in the unwinding direction, but it can be easily unfolded by pulling lightly: △
・ It cannot be deployed without effort. Or even if you apply force, the sheet shape is maintained and it cannot be deployed: ×

The refractory sheets of Examples 1, 2 and 4 to 9 had good self-supporting properties, surface appearance, and expandability. The refractory sheet of Example 3 has a thickness variation in the width direction of ± 0.2 mm and a large heat shrinkage rate, but since the surface of the refractory sheet is uneven, it has self-supporting property, surface appearance, and expandability. Both were good.

The refractory sheet of Comparative Example 1 had a thickness variation of ± 0.2 mm, and the surface was fogged. In Comparative Example 2, in addition to the thickness variation being ± 0.2 mm, the heat shrinkage rate is large, so that winding tightening occurs, and a blocking phenomenon occurs in which the refractory sheet cannot be unwound normally, resulting in poor deployability. It was. In addition, the surface of the refractory sheet became cloudy.

1 ... Winding body, 2, 3 ... Fireproof sheet, 4 ... Embossed unevenness, 5,5a, 5b, 5c ... Rib, 6 ... Matte processing

Claims (5)

Total length Ri der than 2m, a stack of a plurality of refractory sheet comprising a resin composition containing a thermally expandable graphite bar Indah resin, and one of the thermal expansion of the non-thermally expandable graphite inorganic and inorganic fillers A fireproof sheet that includes the body
A refractory sheet having a thickness of 0.5 mm or more and a thickness variation of 0.1 mm or less . The fireproof sheet according to claim 1, wherein the heat shrinkage rate of each of the fireproof sheets before and after heating at 70 ° C. for 22 hours in accordance with JIS K7133 is 1% or less in both the MD direction and the TD direction. The total content of the heat-expandable graphite, the phosphorus compound, the flame retardant and the inorganic filler, which comprises the heat-expandable graphite, the phosphorus compound, the flame retardant and the inorganic filler, is 40 to 40 in the resin composition. The fireproof sheet according to claim 1 or 2, which is 80% by mass. The fireproof sheet according to any one of claims 1 to 3 , wherein the surface of the fireproof sheet is matted. The refractory sheet according to any one of claims 1 to 4 , wherein the temperature of the tan δ peak when the dynamic viscoelasticity is measured at a temperature dispersion (heating rate of 5 ° C./min) under 1 Hz is 80 ° C. or less.

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