JP2019112938A - Fireproof material and its wound body - Google Patents

Abstract

To provide a long polyvinyl chloride fireproof material with improved heat shrinkage ratio.SOLUTION: A fireproof material 2 comprises a fireproof sheet 3 consisting of a polyvinyl chloride resin, a heat expansive graphite and a resin composition and a heat shrinkage ratio under a condition of heat treatment at 60°C and for 6 hours is at most 5%.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 refractory resin composition in which a resin component contains a refractory material is used. Polyvinyl chloride-based resin composition containing a polyvinyl chloride-based resin as a resin component, a phosphorus compound, thermally expandable graphite neutralized, and an inorganic filler Materials are disclosed.

Japanese Patent Application Laid-Open No. 2005-009304

Although the fireproof material which consists of such a polyvinyl-chloride-type resin composition is used in the form of a fireproof sheet, lengthening of a fireproof sheet is demanded from easiness of construction and easiness of parts processing. . However, in order to develop fire resistance, it is common for the refractory material to contain a large amount of raw materials such as thermally expandable graphite and inorganic fillers such as flame retardants. In order to achieve strength to withstand winding and the like for lengthening, it is necessary to fully gelate the polyvinyl chloride resin at the time of kneading and disperse the raw material in the resin, and residual distortion occurs at the time of molding There was a problem that it was easy to happen. Furthermore, since it contains thermally expansive graphite, the temperature can not be raised sufficiently in the molding process, and it is difficult to extend the residual strain relaxation process for a long time. There is a problem that the thermal contraction rate of the composition is increased. As a result, when heat is applied in the manufacturing process of the wound body of the fireproof sheet, there is a problem that peeling occurs due to shrinkage or the dimensions become insufficient.

An object of the present invention is to provide a polyvinyl chloride-based refractory material having a reduced thermal contraction rate 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 thermal contraction rate of 5% or less under the conditions of heat treatment at 60 ° C. for 6 hours.

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

Item 3. The fireproof material according to claim 2, wherein two fireproof sheets having the same or different compositions are adhered via the fiber sheet.

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

The ta between 0-140 ° C which appear when measuring the dynamic viscoelasticity in temperature dispersion under the item 5.1 Hz
The maximum value of ndelta peak is 1.25 or less, The refractory material as described in any one of claim | item 1 -4 characterized by the above-mentioned.

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

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

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

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

According to the present invention, the heat shrinkage of the polyvinyl chloride-based refractory material and the wound body thereof is reduced, so that the handling of the refractory sheet is improved. In addition, the dimensional accuracy of the fireproof sheet after processing such as punching is improved.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic perspective view of the winding body of 1st Embodiment of this invention. The schematic perspective view of the state which extended the winding body of FIG. 1 to the sheet | seat state. The schematic front view of the laminated body of several fireproof sheet. (A) A schematic front view of a fireproof material in which a fiber sheet is sandwiched between two fireproof sheets. (B) A schematic front view showing another example in which the fiber sheet is disposed as the outermost layer of the refractory material. (C) A schematic front view of a fireproofing material in which fiber sheets are adhered to both sides of the fireproof sheet.

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

The wound body 1 of the first embodiment of the present invention shown in FIG. 1 is formed by winding a refractory material 2 formed of a single layer of a fire resistant sheet 3 formed of a fire resistant resin composition containing a vinyl chloride resin. . Figure 2
As shown in FIG. 1, when the wound body 1 of FIG. 1 is extended so that the fireproof sheet 3 becomes flat, X is the length of the fireproof sheet 3, Y is the width of the fireproof sheet 3, and Z is fireproof. Thickness of the elastic 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 fireproof sheet 3 is not particularly limited, but preferably
It is 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 10% or less in thickness variation. The upper limit of thickness Z is preferably 5 mm or less. By thus increasing the thickness and reducing the thickness variation,
The refractory 2 can be made longer.

“MD” refers to the flow direction (MD direction) of the fireproof resin composition at the time of molding of the fireproof sheet 3 and “TD” is a direction perpendicular to the flow direction of the fireproof resin composition (TD direction) Point to.

In FIGS. 1 and 2, although the wound body 1 is extended, it is referred to as a refractory material 2, but the wound body 1 is
The refractory material 2 includes one that is cut in the longitudinal direction and / or the width direction and becomes a part of the wound body 1.

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

The fireproof resin material which comprises the fireproof material 2 is a fireproof resin composition which contains thermally expansible graphite and an inorganic filler in the resin component of polyvinyl chloride system resin.

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

Moreover, as a resin component of the fire resistant resin composition which comprises the refractory material 2, thermoplastic resins other than a polyvinyl chloride type-resin, a thermosetting resin, a rubber substance, and those combination may further be included.

As a thermoplastic resin, for example, polypropylene resin, polyethylene resin, poly (
1-) butene resin, polyolefin resin such as polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate resin, polyphenylene ether resin, (meth) acrylic resin, polyamide resin And synthetic resins such as phenolic resins, polyurethane resins 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.

As the rubber substance, natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber,
Examples thereof include rubber materials such as chlorinated butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, urethane rubber and the like.

One or two or more of these synthetic resins and / or rubber substances can be used.

Thermally expandable graphite is a conventionally known substance that expands when heated, and is a natural scaly graphite,
Powders such as pyrolytic graphite and quiche graphite, inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid, concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, dichromate It is treated with a strong oxidizing agent such as hydrogen peroxide to form a graphite intercalation compound, which is a kind of a crystal compound maintaining the layered structure of carbon.

The thermally expandable graphite obtained by acid treatment as described above may be further neutralized with ammonia, aliphatic lower amines, alkali metal compounds, alkaline earth metal compounds and the like. The particle size of the thermally expandable graphite is preferably 20 to 200 mesh. When the particle size is 200 mesh or less, the degree of expansion of the graphite is sufficient to obtain the expanded heat insulating layer, and when the particle size is 20 mesh or more, the dispersibility in blending with the resin is good and the physical properties are It is good. Examples of commercially available thermally expandable graphite include “GREP-EG” manufactured by Tosoh Corporation, “GRAF manufactured by GRAFTECH”.
"GUARD" and the like.

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

In addition, as inorganic fillers, calcium sulfate, gypsum fiber, calcium salts such as calcium silicate, etc .; silica, diatomaceous earth, dawsonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, 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” ( Lead zirconate titanate, zinc stearate, calcium stearate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydrated sludge and the like. 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
It is μm. When the addition amount of the inorganic filler is small, the dispersibility largely affects the performance, and therefore the inorganic filler having a small particle diameter is preferable, but the dispersibility is good when it is 0.5 μm or more. When the addition amount is large, the viscosity of the refractory resin composition increases and the moldability decreases as the high loading progresses, but the viscosity of the refractory resin composition can be decreased by increasing the particle diameter. From the point of view, those having a large particle diameter are preferable, but a particle diameter of 100 μm or less is desirable in terms of the surface properties of the molded product and the mechanical properties of the fire resistant resin composition.

As an inorganic filler, for example, in aluminum hydroxide, "Hygirite H-31" (made by Showa Denko) with a particle diameter of 18 μm, "B325" (made by ALCOA) with a particle diameter of 25 μm, particle diameter in calcium carbonate 1.8 μm "Whiteton SB red" (made by Bihoku Powder Industry Co., Ltd.), particle size 8
Examples include μm “BF300” (manufactured by Bihoku Powder Industry Co., Ltd.) and the like.

The above-described refractory resin composition contains 10 to 10 parts by weight of thermally expandable graphite relative to 100 parts by weight of the resin component.
Preferably, it comprises 350 parts by weight and 30 to 400 parts by weight of inorganic filler.

In addition, the total of the thermally expandable graphite and the inorganic filler is 5 per 100 parts by weight of the resin component.
A range of 0 to 600 parts by weight is preferred.

The refractory resin composition is expanded by heating to form a refractory heat insulating layer. According to this composition, the thermally expandable refractory material is expanded by heating such as fire, and a required volume expansion coefficient can be obtained, and after expansion, a residue having a predetermined heat insulation performance and a predetermined strength is formed. Stable fire performance can be achieved.

When the total amount of the thermally expandable graphite and the inorganic filler in the above fireproof resin composition is 50 parts by weight or more, sufficient fire resistance performance can be obtained by satisfying the residual amount after combustion, and when it is 600 parts by weight or less Physical properties are maintained.

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

As the plasticizer, for example, di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), diisodecyl phthalate (DI)
Phthalate ester plasticizers such as DP); di-2-ethylhexyl adipate (DOA),
Fatty acid ester based plasticizers such as diisobutyl adipate (DIBA), dibutyl adipate (DBA); epoxidized ester based plasticizers such as epoxidized soybean oil; adipic acid esters,
Polyester plasticizers such as adipic acid polyester; trimellitic ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM); trimethyl phosphate (TMP), triethyl phosphate TE
P ester plasticizers, such as P), etc. are mentioned, These may be used independently and 2 or more types may be used together.

The amount of the plasticizer to be 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. Sufficient impact resistance is acquired as the usage-amount of a plasticizer is 20 weight part or more, and a flame retardance is exhibited as it is 200 weight part or less.

The above-mentioned fireproof resin composition increases the strength of the expansion heat insulation layer to improve the fire resistance performance.
In addition to the above components, it may further contain a phosphorus compound. The phosphorus compound is not particularly limited. For example, red phosphorus; various phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, etc .; sodium phosphate, Metal salts of phosphoric acid such as potassium phosphate and magnesium phosphate; ammonium polyphosphates; compounds represented by the following chemical formula (1) and the like can be mentioned. However, the above-mentioned plasticizers are excluded. Of these, in terms of fire protection performance,
Red phosphorus, ammonium polyphosphates and compounds represented by the following chemical formula (1) are preferable, and ammonium polyphosphates are more preferable in terms of performance, safety, cost and the like.

In Chemical Formula (1), R ¹ and R ^{3 each} 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, having 1 to 1 carbon atoms
6 linear or branched alkyl group, linear or branched alkoxyl group having 1 to 16 carbon atoms, aryl group having 6 to 16 carbon atoms, or aryloxy group having 6 to 16 carbon atoms .

As red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of moisture resistance and safety such as not spontaneously igniting at the time of kneading, one 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 and the like, and ammonium polyphosphate is preferably used in terms of handleability and the like. As a commercial item, for example, Clariant "AP 422", "AP 462", Budenheim Iberica "FR"
CROS 484 "," FR CROS 487 "and the like.

The compound represented by the chemical formula (1) is not particularly limited, and, for example, methyl phosphonic acid,
Dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid,
2,3-Dimethyl-butyl phosphonic acid, octyl phosphonic acid, phenyl phosphonic acid, dioctyl phenyl phosphonate, dimethyl phosphinic acid, methyl ethyl phosphinic acid, methyl propyl phosphinic acid, diethyl phosphinic acid, dioctyl phosphinic acid, phenyl phosphinic acid, diethyl phenyl Phosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid and the like can be mentioned. Among them, t-butyl phosphonic acid is preferable but is expensive in terms of high flame retardancy. 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 used per 100 parts by weight of the resin component:
It is contained so that the total amount of the said phosphorus compound and the said thermally expandable graphite will be 20-400 weight part.

Furthermore, the fire resistant resin composition used in the present invention may be a metal damage inhibitor, in addition to an antioxidant such as phenol type, amine type and sulfur type, as needed, as long as the object of the present invention is not impaired. And additives such as antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins and molding aids, and tackifiers such as polybutene and petroleum resins.

In one embodiment, the fireproof resin composition which constitutes fireproof sheet 3 contains crystalline resin other than polyvinyl chloride resin as a resin ingredient. The crystalline resin refers to a resin having a portion of “crystal” in which molecular chains are regularly arranged among thermoplastic resins. By containing the crystalline resin, the shrinkage of the refractory sheet 3 is suppressed even if heat is applied at the time of manufacturing the wound body 1 of the refractory material 2. 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 is used for the temperature at the time of use of the refractory material 2 including the high temperature in summer
Can be weather resistant. 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 content of the resin component of the fireproof sheet 3 is, for example, 95% by weight to 50% by weight of polyvinyl chloride resin in the resin component constituting the fireproof sheet, and 5% by weight to 45% by weight of the crystalline resin.
Chlorinated polyethylene resin is preferred from the viewpoint of compatibility with polyvinyl chloride resin.

In another embodiment, the fireproof resin composition which comprises fireproof sheet 3 contains resin whose glass transition temperature is 50 ° C or more other than polyvinyl chloride resin as a resin ingredient. By containing a resin having a glass transition temperature of 50 ° C. or more, the shrinkage of the fireproof sheet 3 is suppressed even if heat is applied at the time of manufacturing the wound body 1 of the fireproof material 2. Moreover, it is advantageous also in the point of the weather resistance at the time of use of the fireproof sheet 3. FIG. Examples of the resin having a glass transition temperature of 50 ° C. or higher include polymethacrylate or copolymer thereof or modified product thereof, polymethyl methacrylate resin (PMMA), polyethylene terephthalate (PET) and the like. The content of the resin component of the fireproof sheet 3 is, for example, 95% by weight to 5% by weight of polyvinyl chloride resin in the resin component constituting the fireproof sheet
The resin having a glass transition temperature of 50 ° C. or higher is 5% by weight to 45% by weight. From the viewpoint of compatibility with polyvinyl chloride resin, polymethacrylate or a copolymer thereof or a modified product thereof is preferred.

The resin composition is not particularly limited as long as the resin composition is thermally insulated by the expanded layer when exposed to high temperatures during a fire and the like and the expanded layer has a strength, but under a heating condition of 50 kW / m ² It is preferable that 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 burnout portion of the resin component,
When the strength is 50 times or less, the strength of the expansion layer is maintained, and the effect of preventing penetration of the flame is maintained.

Each component of the fire resistant resin composition is kneaded using a known apparatus such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a roll mill, a planetary stirrer, a nip roll, a calendar roll, etc. The sheet is formed by passing the kneaded material through a predetermined clearance between rolls. The fire-resistant material 2 is obtained by winding up the obtained sheet molded product with a winding roll.
Can be obtained as the wound body 1. At the time of winding, it is desirable to control the winding tension and to minimize the distortion at the time of winding by the conventionally known technique.

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 contraction rate of 5% under the conditions of heat treatment at 60 ° C. for 6 hours. It is below. The degree of the thermal contraction rate in the heat treatment at 60 ° C. for 6 hours is an index for evaluating the 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 wound body of the fireproof sheet, peeling due to shrinkage and lack of dimensions are suppressed.

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

The thermal contraction rate of the refractory material 2 can be realized by those skilled in the art by appropriately selecting the amounts of the thermally expandable graphite, the phosphorus compound, the plasticizer, and the inorganic filler with respect to the polyvinyl chloride resin.
From the viewpoint of reducing stress strain relaxation components and increasing elastic components, the total amount of the inorganic filler and the expansion-initiating graphite relative to the resin component (including a plasticizer when the plasticizer is included in the resin composition) It is preferable that it is equal or more. Furthermore, from the viewpoint of reducing the relaxation component, the resin component is preferably 35% by mass or less of the resin composition (refractory sheet when the resin composition is a refractory sheet), and polyvinyl chloride resin is 35% of the resin composition. It is more preferable that the content is at most mass%.

Optionally, the thermal contraction rate of the refractory material 2 can be further improved by annealing at the time of production 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 this, the thermal contraction rate of the refractory material 2 can be reduced.

Moreover, preferably, the maximum value of the tan-delta peak between 0-140 degreeC at the time of measuring the dynamic viscoelasticity in temperature dispersion by 1 Hz is 1.25 or less in the refractory material 2 of this invention. According to this configuration, ta
The lower the value of nδ, the stronger the elastic component, and the smaller the residual strain produced in the production of the refractory material. As a result, peeling due to shrinkage and dimensional insufficiency are suppressed.

The refractory material 2 can be used to provide fire resistance to structures such as windows, shoji, doors (i.e., doors), doors, doors, brans, fixtures such as inter-rows; ships; and structures such as elevators. It is used in particular for the sealing and fire protection of the openings or gaps of these structures. For example, the refractory material 2 can be used as an airtight material such as a tight material or a sealing material for improving the airtightness or water tightness of a fitting. The structure may be made of any material such as metal, synthetic resin, wood, or a combination thereof. Note that "opening" refers to an opening that exists between or in the structure and another structure, and "gap" refers to an opening that occurs between two opposing members or portions of the opening.

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

  The refractory material 2 may be provided with another optional additional layer other than the fireproof sheet 3 of FIG.

The fireproof material 2 may be a composite fireproof material made of a plurality of the fireproof sheets 3 as shown in FIG. 3 instead of being made up of a single fireproof sheet 3 as shown in FIG. When the fireproof material 2 is comprised from the several said fireproof sheet 3, each of the fireproof sheet 3 may be comprised from the fireproof resin composition of the same composition, and may be comprised from another fireproof resin composition. Good. For example, one layer of the fireproof sheet 3 may be a layer containing a polyvinyl chloride resin and a crystalline resin, and the other layer may be a layer containing a polyvinyl chloride resin but not the crystalline resin. One layer of the fire resistant sheet 3 is a layer containing polyvinyl chloride resin and resin having a glass transition temperature of 50 ° C. or higher, and the other layer contains polyvinyl chloride resin but does not contain a resin having a glass transition temperature of 50 ° C. or higher It may be a layer. Also when the fireproof material 2 is comprised from the several said fireproof sheet 3, the fireproof material 2 may be equipped with another arbitrary additional layers other than the fireproof sheet 3. As shown in FIG.

The lamination may be performed by bonding a plurality of fireproof sheets 3 with an adhesive means or the like, or may be performed by a known technique such as thermocompression bonding or integral molding. Also in this case, it is preferable to make the thickness of the fireproof material 2 which consists of several fireproof sheet 3 the same as Z of FIG.

In order to suppress the thermal contraction of the refractory material 2, as shown in FIG. 4A, the layer of the fiber sheet 4 as the base material layer is sandwiched between two fire resistant sheets 3 as shown in FIG. It may be configured as a composite refractory material. Furthermore, as shown in FIG. 4 (b), the fireproof material 2 may be formed as a composite fireproof material in which the fiber sheet 4 is laminated with one or more fireproof sheets 3 and the fiber sheet 4 is disposed as the outermost layer. Furthermore, as shown to FIG. 4C, 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 metal fiber material, and may be a woven or non-woven fabric, and may or may not be a non-combustible material. For example, as a material constituting the fiber sheet 4, woven fabric of glass fiber (glass cloth, roving cloth, continuous strand mat, etc.)
Or nonwoven fabric (chopped strand mat etc.), woven fabric of ceramic fibers (ceramic cloth etc.) or nonwoven fabric (ceramic mat etc.), carbon fiber woven fabric or nonwoven fabric, or sheet-like net or mat formed from metal mesh 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 the thermal contraction of the refractory material 2 is suppressed.

EXAMPLES Although an Example is given to the following and this invention is more concretely demonstrated to it, this invention is not limited to these.

1. Method of Producing Refractory Material The refractory materials of Examples 1 to 20 and Comparative Example 1 were produced with the formulations shown in Table 1. The unit of each component in the table is part by mass.

The mixture shown in Table 1 is mixed by a kneader, and the mixture is formed into a sheet by a calender roll, and a fireproof sheet as a fireproof resin molded product having a width of 150 mm, a thickness of 1.5 mm and a length of 5 m. Obtained. In addition, the kneader temperature was 130 ° C., and the kneading time in the kneader was standardized to 5 minutes after the graphite was introduced.

In Examples 1, 3, 16, and 17, the fire resistant resin formed of the fire resistant resin composition containing the vinyl chloride resin of formulation (1), and the fire resistant resin containing the vinyl chloride resin of formulation (2) A fire resistant sheet formed from the composition was made. The resin composition was kneaded with a kneader at 130 ° C., and was formed into a sheet having a thickness of 0.75 mm by a calender roll. Glass paper as a base material for two fireproof sheets produced in this way (60 g per square meter, 50 μm thickness)
(Examples 1 and 3) or PET nonwoven fabric (Examples 16 and 17) via nip roll 1
It adhered at 20 ° C and 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 vinyl chloride resin of formulation (1), and the fireproof material was produced.

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

2. Measurement of Heat Shrinkage Rate From the refractory materials of Examples 1 to 20 and Comparative Example 1, evaluation samples of 100 mm square were cut out along the MD and TD directions. The sample extraction position was cut out from the center of the center length (3 m). Draw three lines at a time in the MD and TD directions of the cut sample
. The lengths of each line before and after the heat treatment were measured at positions of 5 cm, 5 cm, and 7.5 cm, for a total of 6). 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. The measured value was calculated by the average value of three points for each direction. The results are shown in Table 1.
Thermal shrinkage (%) = (length before heat treatment−length after heat treatment) / length before heat treatment × 100

3. tan δ measurement The obtained refractory sheet is cut into a circle having a diameter of 20 mm, and sheared using a visco-elasticity measuring apparatus ("ARES" manufactured by Rheometrics Co., Ltd.) under the condition of 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 heating rate of 5 ° C./min.
The maximum value of tan δ in the temperature range was measured.

In the refractory material of Examples 1 to 20, the MD shrinkage ratio is as low as 5% or less, and the refractory material of Comparative Example 1 is 5%.
It was over. Moreover, in the refractory material of Examples 1-20, the maximum value of a tan-delta peak was 1.25 or less.

  1 ... wound 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 thermal contraction rate of 5% or less under the conditions of heat treatment at 60 ° C. for 6 hours.   The fireproof material according to claim 1, wherein a fiber sheet is further adhered to the fireproof sheet. The fireproof material according to claim 2, wherein two fireproof sheets having the same or different compositions are adhered via the fiber sheet. The fireproof material according to claim 2 or 3, wherein the fiber sheet is adhered to one side or both sides of the fireproof sheet. The maximum value of tan δ peak between 0 to 140 ° C., which appears when measuring dynamic viscoelasticity at temperature dispersion under 1 Hz, is 1.25 or less. Refractory material 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 according to any one of claims 1 to 5, which contains a resin having a glass transition temperature of 50 ° C or more. The polyvinyl chloride resin is 35 mass% or less of a fireproof sheet, It is characterized by the above-mentioned.
The refractory material as described in any one of 7.   The wound body which winds the refractory material as described in any one of Claims 1-8.

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