JP2017141661A - Refractory material and wound body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl chloride refractory material that is long and has an improved thermal shrinkage.SOLUTION: A refractory material 2 has a refractory sheet 3 that comprises a resin composition comprising polyvinyl chloride resin and thermally expandable graphite, and has a thermal shrinkage of 5% or less under the condition of heated at 60°C for 6 hours.SELECTED DRAWING: Figure 2

Description

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

  In order to impart fire resistance to a structure such as a house, conventionally, a thermally expandable refractory material made of a fire resistant resin composition containing a fire resistant material in a resin component has been used. A polyvinyl chloride resin composition containing a polyvinyl chloride resin as a resin component, a phosphorus compound, neutralized heat-expandable graphite, and an inorganic filler, and a heat-expandable refractory that is a press-molded product thereof A material is disclosed.

JP2005-009304

  Although a refractory material made of such a polyvinyl chloride resin composition is used in the form of a refractory sheet, it is desired to lengthen the refractory sheet for ease of construction and ease of parts processing. . However, the refractory material generally contains a large amount of raw materials such as thermally expandable graphite and an inorganic filler such as a flame retardant in order to develop the fire resistance. In order to increase the length, it is necessary to sufficiently gel the polyvinyl chloride resin at the time of kneading and to disperse the raw material in the resin in order to obtain a strength that can withstand winding and the like. There was a problem that occurred easily. Furthermore, since it contains heat-expandable graphite, the temperature cannot be raised sufficiently in the molding process, and it is difficult to make the residual strain relaxation process a long time. There was a problem that the thermal contraction rate of the composition was increased. As a result, there is a problem that when heat is applied in the manufacturing process of the wound body of the refractory sheet, peeling due to shrinkage occurs or the dimensions become insufficient.

  An object of the present invention is to provide a polyvinyl chloride refractory material having a reduced thermal shrinkage and a wound body thereof.

  Item 1. A refractory material comprising a refractory sheet comprising a resin composition containing a polyvinyl chloride resin and thermally expandable graphite, and having a heat shrinkage rate of 5% or less under conditions of heat treatment at 60 ° C. for 6 hours.

  Item 2. Item 2. The refractory material according to Item 1, wherein a fiber sheet is further bonded to the refractory sheet.

  Item 3. Item 2. The refractory material according to item 2, wherein two refractory sheets having the same composition or different from each other are bonded together via the fiber sheet.

  Item 4. Item 4. The refractory material according to Item 2 or 3, wherein the fiber sheet is bonded to one side or both sides of the refractory sheet.

  Any one of Items 1 to 4, wherein the maximum value of the tan δ peak between 0 to 140 ° C. that appears when dynamic viscoelasticity at temperature dispersion is measured under the term 5.1 Hz is 1.25 or less. The refractory material according to one item.

  Item 6. Item 6. The refractory material according to any one of Items 1 to 5, comprising a crystalline resin having a melting point temperature of 50 ° C or higher.

  Item 7. Item 6. The refractory material according to any one of Items 1 to 5, comprising a resin having a glass transition temperature of 50 ° C or higher.

  Item 8. The refractory material according to any one of claims 1 to 7, wherein the polyvinyl chloride component is 35 mass% or less of the refractory sheet.

    Item 9. Item 10. A wound body obtained by winding the refractory material according to any one of Items 1 to 8.

  According to the present invention, since the heat shrinkage of the polyvinyl chloride refractory material and its wound body is reduced, the handling of the refractory sheet is improved. Moreover, the dimensional accuracy of the fireproof sheet after processing such as punching is improved.

The schematic perspective view of the winding body of 1st Embodiment of this invention. The schematic perspective view of the state which extended the wound body of FIG. 1 to the sheet | seat state. The schematic front view of the laminated body of a several fireproof sheet. (A) The schematic front view of the refractory material in which the fiber sheet is pinched | interposed between two refractory sheets. (B) The schematic front view which shows the other example which has arrange | positioned the fiber sheet as an outermost layer of a refractory material. (C) The schematic front view of the refractory material by which the fiber sheet is adhere | attached on both surfaces of the refractory sheet.

  A first embodiment in which the present invention is embodied in a long sheet-like refractory material and its wound body will be described with reference to FIGS.

  A wound body 1 of the first embodiment of the present invention shown in FIG. 1 is formed by winding a refractory material 2 composed of a single refractory sheet 3 formed from a refractory resin composition containing a vinyl chloride resin. . As shown in FIG. 2, when the wound body 1 of FIG. 1 is extended so that the refractory sheet 3 is planar, X is the length of the refractory sheet 3, Y is the width of the refractory sheet 3, Z Is the thickness of the refractory sheet 3. In the present invention, the total length X of the refractory sheet 3 (that is, the refractory material 2) is 20 m or more, and the upper limit is preferably 800 m or less. The width Y of the refractory sheet 3 is not particularly limited, but is preferably 1 mm or more and 2 m or less. The thickness Z of the refractory sheet 3 is not particularly limited, but is preferably 0.2 mm or more, and the thickness variation is 10% or less. The upper limit value of the thickness Z is preferably 5 mm or less. Thus, the refractory material 2 can be elongated by increasing the thickness and reducing the thickness variation.

  “MD” refers to the flow direction (MD direction) of the refractory resin composition during molding of the refractory sheet 3, and “TD” refers to the direction perpendicular to the flow direction of the refractory resin composition (TD direction). Point to.

  In FIGS. 1 and 2, the rolled body 1 is referred to as a refractory material 2, but the wound body 1 is cut in the longitudinal direction and / or the width direction to become a part of the wound body 1. The refractory material 2 is also included.

  Hereinafter, the refractory resin material constituting the refractory material 2 will be described in detail.

  The refractory resin material constituting the refractory material 2 is a refractory resin composition containing a thermally expandable graphite and an inorganic filler in a resin component of a polyvinyl chloride resin.

  Examples of the resin component polyvinyl chloride resin include, for example, a polyvinyl chloride homopolymer; a copolymer of a vinyl chloride monomer and a monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer; Examples include graft copolymers obtained by graft copolymerization of vinyl chloride with (co) polymers, and these may be used alone or in combination of two or more. Furthermore, the polyvinyl chloride may be chlorinated. The chlorinated vinyl chloride resin can be obtained by post-chlorinating a polyvinyl chloride resin or a vinyl chloride copolymer. The chlorinated vinyl chloride resin is described in, for example, JP-A-9-227747.

  The resin component of the refractory resin composition constituting the refractory material 2 may further include a thermoplastic resin other than the polyvinyl chloride resin, a thermosetting resin, a rubber substance, and a combination thereof.

  Examples of the thermoplastic resin include polypropylene resins, polyethylene resins, poly (1-) butene resins, polyolefin resins such as polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, and polycarbonates. And synthetic resins such as polyresin, polyphenylene ether resin, (meth) acrylic resin, polyamide resin, phenolic resin, polyurethane resin, and polyisobutylene.

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

  Rubber materials 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 And rubber materials such as epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicon rubber, fluororubber, and urethane rubber.

  These synthetic resins and / or rubber substances can be used alone or in combination of two or more.

  Thermally expandable graphite is a conventionally known substance that expands when heated, and powders such as natural scaly graphite, pyrolytic graphite, and quiche graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, excess A graphite intercalation compound produced by treatment with a strong oxidizing agent such as chloric acid, perchlorate, permanganate, dichromate, dichromate, hydrogen peroxide, etc. A type of crystalline compound that maintains its structure.

  The heat-expandable graphite obtained by 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 thermally expandable graphite is preferably 20 to 200 mesh. When the particle size is 200 mesh or smaller, the degree of expansion of the graphite is sufficient to obtain an expanded heat insulating layer, and when the particle size is 20 mesh or larger, the dispersibility when blended in the resin is good and the physical properties are It is good. Examples of commercially available products of thermally expandable graphite include “GREP-EG” manufactured by Tosoh Corporation, “GRAFGUARD” manufactured by GRAFTECH, and the like.

  When the expanded heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and works as an aggregate to improve the strength of the expanded heat insulating layer. The inorganic filler is not particularly limited, and examples thereof include 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 Hydrous minerals such as aluminum hydroxide and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate and barium carbonate; inorganic phosphates as flame retardants .

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

  As a particle size of an inorganic filler, 0.5-100 micrometers is preferable, More preferably, it is 1-50 micrometers. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance, so that the particle size is preferably small, but if it is 0.5 μm or more, the dispersibility is good. When the addition amount is large, the viscosity of the refractory resin composition increases and the moldability decreases as the high filling proceeds, but the viscosity of the refractory resin composition can be decreased by increasing the particle size. From the point of view, those having a large particle size are preferred, but a particle size of 100 μm or less is desirable from the viewpoint of the surface properties of the molded article and the mechanical properties of the fireproof resin composition.

  As the inorganic filler, for example, for aluminum hydroxide, “Hijilite H-31” (manufactured by Showa Denko) having a particle size of 18 μm, “B325” (manufactured by ALCOA) having a particle size of 25 μm, and calcium carbonate, Examples include 1.8 μm “Whiteon SB Red” (manufactured by Bihoku Powdered Industries Co., Ltd.), “BF300” (manufactured by Bihoku Powdered Industries Co., Ltd.) having a particle size of 8 μm, and the like.

  The refractory resin composition preferably contains 10 to 350 parts by weight of thermally expandable graphite and 30 to 400 parts by weight of an inorganic filler with respect to 100 parts by weight of the resin component.

  The total of the thermally expandable graphite and the inorganic filler is preferably in the range of 50 to 600 parts by weight with respect to 100 parts by weight of the resin component.

  The refractory resin composition expands by heating to form a refractory heat insulating layer. According to this composition, the thermally expandable refractory material expands by heating such as a fire, and can obtain a necessary volume expansion coefficient. After expansion, a residue having a predetermined heat insulation performance and a predetermined strength is formed. It is also possible to achieve stable fireproof performance.

  When the total amount of the thermally expandable graphite and the inorganic filler in the above refractory resin composition is 50 parts by weight or more, a sufficient amount of fire resistance can be obtained by satisfying the amount of residues after combustion. The physical properties are maintained.

  The refractory resin composition may further contain a plasticizer in addition to the components described above. The plasticizer acts as a processing aid when the resin component is a polyvinyl chloride resin.

  Examples of the plasticizer include phthalate plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), diisodecyl phthalate (DIDP), etc .; di-2-ethylhexyl adipate (DOA), fatty acid ester plasticizers such as diisobutyl adipate (DIBA), dibutyl adipate (DBA); epoxidized ester plasticizers such as epoxidized soybean oil; polyester plasticizers such as adipic acid esters and adipic acid polyesters; 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) Etc., and these can be used alone, or two or more kinds may be used in combination.

  The amount of the plasticizer used is preferably 20 to 200 parts by weight and more preferably 30 to 100 parts by weight with respect to 100 parts by weight of the resin component. When the amount of the plasticizer used is 20 parts by weight or more, sufficient impact resistance is obtained, and when it is 200 parts by weight or less, flame retardancy is exhibited.

  The fireproof resin composition may further contain a phosphorus compound in addition to the components described above in order to increase the strength of the expanded heat insulating layer and improve the fireproof performance. The phosphorus compound is not particularly limited. For example, red phosphorus; various phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate; sodium phosphate, Examples thereof include metal phosphates such as potassium phosphate and magnesium phosphate; ammonium polyphosphates; compounds represented by the following chemical formula (1), and the like. However, the above plasticizer is excluded. Of these, red phosphorus, ammonium polyphosphates, and compounds represented by the following chemical formula (1) are preferable from the viewpoint of fireproof performance, and ammonium polyphosphates are more preferable in terms 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. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon. The aryloxy group of Formula 6-16 is represented.

  As red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of safety such as moisture resistance and not spontaneously igniting during kneading, a material in which the surface of red phosphorus particles is coated with a resin is preferably used. The ammonium polyphosphates are 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, “FR CROS 484” and “FR CROS 487” manufactured by Budenheim Iberica.

  The compound represented by the chemical formula (1) is not particularly limited. For example, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t- Butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphine Examples include acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid and the like. 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.

  When a phosphorus compound is used, for example, the phosphorus compound is contained so that the total amount of the phosphorus compound and the thermally expandable graphite is 20 to 400 parts by weight with respect to 100 parts by weight of the resin component.

  Further, the refractory resin composition used in the present invention is a range that does not impair the object of the present invention, and if necessary, in addition to antioxidants such as phenols, amines, sulfurs, etc. , Additives such as antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, molding aids, and tackifiers such as polybutenes and petroleum resins.

  In one embodiment, the refractory resin composition constituting the refractory sheet 3 contains a crystalline resin in addition to the polyvinyl chloride resin as a resin component. The crystalline resin refers to a resin having a “crystal” portion in which molecular chains are regularly arranged among thermoplastic resins. By containing crystalline resin, even if heat is applied at the time of manufacture of the wound body 1 of the refractory material 2, shrinkage of the refractory sheet 3 is suppressed. Preferably, the melting point temperature of the crystalline resin is 50 ° C. or higher. When the melting point temperature of the crystalline resin is 50 ° C. or higher, the refractory material 2 can have weather resistance with respect to the temperature at the time of use of the refractory material 2 including high temperatures in summer. Examples of the crystalline resin include polyethylene (PE) resin, polyethylene terephthalate (PET) resin, polypropylene (PP) resin, chlorinated polyethylene resin, polyamide (PA) resin, polyacetal (POM) resin, and the like. The resin component content of the refractory sheet 3 is, for example, 95% to 50% by weight of the polyvinyl chloride resin in the resin component constituting the refractory sheet and 5% to 45% by weight of the crystalline resin. From the viewpoint of compatibility with the polyvinyl chloride resin, a chlorinated polyethylene resin is preferred.

  In another embodiment, the refractory resin composition constituting the refractory sheet 3 contains, as a resin component, a resin having a glass transition temperature of 50 ° C. or higher in addition to the polyvinyl chloride resin. By containing a resin having a glass transition temperature of 50 ° C. or more, even when heat is applied during the production of the wound body 1 of the refractory material 2, the shrinkage of the refractory sheet 3 is suppressed. Moreover, it is also advantageous in terms of weather resistance when the fireproof sheet 3 is used. Examples of the resin having a glass transition temperature of 50 ° C. or higher include polymethacrylate or a copolymer thereof or a modified product thereof, polymethyl methacrylate resin (PMMA), polyethylene terephthalate (PET), and the like. The content of the resin component of the refractory sheet 3 is, for example, 95% by weight to 5% by weight of the polyvinyl chloride resin in the resin component constituting the refractory sheet, and 5% by weight of the resin having a glass transition temperature of 50 ° C. or higher. ~ 45 wt%. From the viewpoint of compatibility with the polyvinyl chloride resin, polymethacrylate, a copolymer thereof or a modified product thereof is preferable.

The resin composition is not particularly limited as long as it is thermally insulated by the expanded layer when exposed to a high temperature such as a fire, and has the strength of the expanded layer, but under a heating condition of 50 kW / m ^2. It is preferable if the volume expansion coefficient 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-out portion of the resin component, and when it is 50 times or less, the strength of the expansion layer is maintained and flame penetration is prevented. Effect is maintained.

  Each component of the refractory resin composition is kneaded using a known apparatus such as a single-screw extruder, twin-screw extruder, Banbury mixer, kneader mixer, kneading roll, reiki machine, planetary stirrer, nip roll, calendar roll, etc. Then, the kneaded material is passed through a clearance between predetermined rolls to form a sheet. The fire-resistant material 2 can be obtained as the wound body 1 by winding the obtained sheet molded product with a winding roll. At the time of winding, it is desirable to control the winding tension by a conventionally known technique so as to minimize the distortion during winding.

  The refractory material 2 of the present invention provided with a refractory sheet comprising a resin composition containing a polyvinyl chloride resin and thermally expandable graphite has a thermal shrinkage rate of 5% under the conditions of heat treatment at 60 ° C. for 6 hours. It is as follows. The degree of thermal shrinkage in the heat treatment at 60 ° C. for 6 hours is an index for evaluating resistance to temperature when the refractory material 2 is used. According to this configuration, even if heat is applied in the manufacturing process of the roll of the refractory sheet, peeling due to shrinkage and lack of dimensions are suppressed.

  The heat shrinkage ratio of the refractory material 2 (fireproof sheet 3) of the present invention is preferably 5% or less in the MD direction, more preferably 3% or less, even more preferably 1% or less, and preferably 1% in the TD direction. It is as follows.

  The heat shrinkage ratio of the refractory material 2 can be realized by those skilled in the art by appropriately selecting the amounts of thermally expandable graphite, phosphorus compound, plasticizer, and inorganic filler with respect to the polyvinyl chloride resin. From the viewpoint of reducing the stress strain relaxation component and increasing the elastic component, the total amount of inorganic filler and expansion-initiating graphite is relative to the resin component (when the plasticizer is included in the resin composition, also includes the plasticizer). It is preferable that the amount is equal to or more. Further, from the viewpoint of reducing the relaxation component, the resin component is preferably 35% by mass or less of the resin composition (when the resin composition is a refractory sheet), the polyvinyl chloride resin is 35% of the resin composition. It is more preferable that the amount is not more than mass%.

  Optionally, the thermal shrinkage of the refractory material 2 can be further improved by annealing during the manufacture of the refractory resin composition, for example, annealing the refractory resin composition at a temperature of 110 ° C. for about 30 minutes to 2 hours. By doing, the thermal contraction rate of the refractory material 2 can be reduced.

  Also preferably, the refractory material 2 of the present invention has a maximum tan δ peak of 0 to 140 ° C. when the dynamic viscoelasticity at 1 Hz is measured with temperature dispersion is 1.25 or less. According to this configuration, the lower the value of tan δ, the stronger the elastic component, so that the residual strain generated during the production of the refractory material tends to be small, and as a result, peeling due to shrinkage and lack of dimensions are suppressed.

  The refractory material 2 can be used to impart fire resistance to structures such as doors, shojis, doors (ie doors), doors, brans, and railings; ships; and structures such as elevators. In particular, they are used to seal and fireproof openings or gaps in these structures. For example, the refractory material 2 can be used as an airtight material such as a tight material or a seal material for improving the airtightness or watertightness of the joinery. The structure may be made of any material such as metal, synthetic resin, wood, or a combination thereof. Note that the “opening” refers to an opening existing between or in a structure and another structure, and the “gap” refers to an opening generated between two members or portions facing each other in the opening.

  As mentioned above, although this invention was demonstrated regarding the wound body 1 and the refractory material 2 of 1st Embodiment, this invention is not restricted to this, The following various deformation | transformation are possible.

  The refractory material 2 may include another arbitrary additional layer other than the refractory sheet 3 of FIG.

  The refractory material 2 may be a composite refractory material composed of a plurality of the refractory sheets 3 as shown in FIG. 3 instead of being composed of a single refractory sheet 3 as shown in FIG. When the refractory material 2 is composed of a plurality of the refractory sheets 3, each of the refractory sheets 3 may be composed of a refractory resin composition having the same composition, or may be composed of another refractory resin composition. Good. For example, one layer of the refractory sheet 3 may be a layer including a polyvinyl chloride resin and a crystalline resin, and the other layer may be a layer including a polyvinyl chloride resin but not including a crystalline resin. One layer of the refractory sheet 3 is a layer including a polyvinyl chloride resin and a resin having a glass transition temperature of 50 ° C. or higher, and the other layer includes a polyvinyl chloride resin but does not include a resin having a glass transition temperature of 50 ° C. or higher. It is good also as a layer. Even when the refractory material 2 is composed of a plurality of the refractory sheets 3, the refractory material 2 may include another arbitrary additional layer other than the refractory sheet 3.

  Lamination may be performed by bonding a plurality of refractory sheets 3 with an adhesive means such as an adhesive, or may be performed by a known technique such as thermocompression bonding or integral molding. Also in this case, it is preferable that the thickness of the refractory material 2 composed of the plurality of refractory sheets 3 is the same as Z in FIG.

  In order to suppress the heat shrinkage of the refractory material 2, the layer of the fiber sheet 4 as the base material layer is sandwiched between the two refractory sheets 3 as shown in FIG. It is good also as a structure of a composite refractory material. Furthermore, as shown in FIG.4 (b), the fireproof material 2 is good also as a structure of the composite fireproof material which laminated | stacked the fiber sheet 4 with the 1 or several fireproof sheet 3, and has arrange | positioned the fiber sheet 4 as an outermost layer. Furthermore, as shown in FIG.4 (c), the fiber sheet 4 may be adhere | attached on both surfaces of the fireproof sheet 3. As shown in FIG. The fiber sheet 4 may be a single layer or a plurality of layers, and the thickness is not limited, and may be, for example, 0.01 mm to 1 mm. The fiber material constituting the fiber sheet 4 is preferably an inorganic fiber or a metal fibrous material, and may be a woven fabric or a nonwoven fabric, and may or may not be a nonflammable material. For example, as a material constituting the fiber sheet 4, glass fiber woven fabric (glass cloth, roving cloth, continuous strand mat, etc.) or non-woven fabric (chopped strand mat, etc.), ceramic fiber woven fabric (ceramic cloth, etc.) or A non-woven fabric (ceramic mat or the like), a woven or non-woven fabric of carbon fiber, or a sheet-like net or mat formed from a wire mesh is preferably used.

  The fireproof sheet 3 and the fiber sheet 4 may be bonded by a known technique such as an adhesive, thermocompression bonding or integral molding. By providing such a fiber sheet 4, the strength of the refractory material 2 is reinforced and thermal contraction of the refractory material 2 is suppressed.

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

1. Production method of refractory material The refractory materials of Examples 1 to 20 and Comparative Example 1 were produced with the formulation shown in Table 1. The unit of each component in the table is part by mass.

  After mixing the composition shown in Table 1 with a kneader, the mixture was formed into a sheet with a calender roll, and a fire-resistant sheet as a fire-resistant resin molded body having a width of 150 mm, a thickness of 1.5 mm, and a length of 5 m was obtained. Obtained. In addition, the kneader temperature was 130 ° C., and the kneading time in the kneader was unified to 5 minutes after the graphite was added, and the test was conducted.

  In Examples 1, 3, 16, and 17, a refractory sheet formed from the refractory resin composition containing the vinyl chloride resin of Formula (1) and the refractory resin containing the vinyl chloride resin of Formula (2) A refractory sheet formed from the composition was prepared. The resin composition was kneaded with a kneader at 130 ° C. and molded into a sheet having a thickness of 0.75 mm with a calendar roll. By using nip rolls through the glass paper (the basis weight of 60 g, thickness of 50 μm) (Examples 1 and 3) or the PET nonwoven fabric (Examples 16 and 17) as base materials using the two fireproof sheets thus produced Bonding at 120 ° C. produced a refractory material.

  In Example 2, the glass paper as a base material was adhere | attached on both surfaces of the fireproof sheet formed from the fireproof resin composition containing the vinyl chloride resin of a mixing | blending (1), and the fireproof material was produced.

  In Examples 4 to 15, 18 to 20, and Comparative Example 1, a refractory material composed of a single layer of a refractory sheet formed from a refractory resin composition containing the vinyl chloride resin of Formula (1) was produced.

2. Measurement of Thermal Shrinkage A 100 mm square evaluation sample was cut out from the refractory materials of Examples 1 to 20 and Comparative Example 1 along the MD and TD directions. The sample removal position was cut out from the center of the length center (3 m). Three lines were drawn in the MD direction and TD direction of the cut sample (positions of 2.5 cm, 5 cm, and 7.5 cm from the outer side, a total of 6 lines), and the length of each line before and after the heat treatment was measured. . The measurement was performed with a digital caliper. It heat-processed at 60 degreeC for 6 hours, and measured the thermal contraction rate according to the following formula | equation. The measured value was calculated by the average value of three points for each direction. The results are shown in Table 1.
Heat shrinkage rate (%) = (length before heat treatment−length after heat treatment) / length before heat treatment × 100

3. tan δ measurement The obtained fire-resistant sheet was cut out into a circle with a diameter of 20 mm, and using a viscoelasticity measuring device (“ARES” manufactured by Rheometrics Co., Ltd.), using a shear method, with a strain amount of 1.0% and a frequency of 1 Hz, Temperature dispersion measurement of dynamic viscoelasticity was performed in the range of 0 ° C. to 140 ° C. at a temperature rising rate of 5 ° C./min. The maximum value of tan δ in the temperature range was measured.

  In the refractory materials of Examples 1 to 20, the MD shrinkage rate was as low as 5% or less, and in the refractory material of Comparative Example 1, it exceeded 5%. Moreover, in the refractory materials of Examples 1 to 20, the maximum value of the tan δ peak was 1.25 or less.

  DESCRIPTION OF SYMBOLS 1 ... Rolled body, 2 ... Fireproof material, 3 ... Fireproof sheet, 4 ... Fiber sheet.

Claims (9)

  A refractory material comprising a refractory sheet comprising a resin composition containing a polyvinyl chloride resin and thermally expandable graphite, and having a heat shrinkage rate of 5% or less under conditions of heat treatment at 60 ° C. for 6 hours.   The refractory material according to claim 1, wherein a fiber sheet is further bonded to the refractory sheet.   The refractory material according to claim 2, wherein two refractory sheets having the same composition or different from each other are bonded together via the fiber sheet.   The refractory material according to claim 2 or 3, wherein the fiber sheet is bonded to one side or both sides of the refractory sheet.   5. The maximum value of the tan δ peak between 0 to 140 ° C. that appears when measuring dynamic viscoelasticity at 1 Hz under temperature dispersion is 1.25 or less. 6. Refractory material as described in   The refractory material as described in any one of Claims 1-5 containing crystalline resin whose melting | fusing point temperature is 50 degreeC or more.   The refractory material as described in any one of Claims 1-5 containing resin whose glass transition temperature is 50 degreeC or more.   The refractory material according to any one of claims 1 to 7, wherein the polyvinyl chloride resin is 35 mass% or less of the refractory sheet.   The wound body formed by winding the refractory material as described in any one of Claims 1-8.

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