JP2019167541A - Thermally-expandable refractory sheet - Google Patents

Abstract

To provide a thermally-expandable refractory sheet that has excellent refractory properties, and alleviates or eliminates the problems caused by an organic solvent blended therein.SOLUTION: A thermally-expandable refractory sheet contains a thermoplastic resin and thermally-expandable graphite. The refractory sheet contains one or more organic solvents, and the content of each organic solvent is 0.01 mass% or less.SELECTED DRAWING: None

Description

  The present invention relates to a thermally expandable fireproof sheet.

  Currently, in the construction field, in order to impart fire resistance performance to building materials such as joinery, columns, and wall materials, a fire resistant sheet in which a thermally expandable inorganic material is mixed into a resin is used. Such a refractory sheet burns and expands by heating, and the combustion residue forms a refractory heat insulating layer, and exhibits refractory heat insulating performance.

  Patent Document 1 describes a refractory resin composition comprising 100 parts by weight of an epoxy resin, 10 to 300 parts by weight of neutralized thermally expandable graphite and 50 to 500 parts by weight of an inorganic filler. Yes.

Patent Document 2 contains a polyvinyl chloride resin containing a phosphorus compound, neutralized thermally expandable graphite, and an inorganic filler, each content of which is the polyvinyl chloride resin 1
The total amount of phosphorus compound and neutralized thermally expandable graphite with respect to 00 parts by weight is 20 to 200 parts by weight, the inorganic filler is 30 to 500 parts by weight, and neutralized thermally expandable graphite: It describes a polyvinyl chloride resin composition in which the weight ratio of the phosphorus compound is 9: 1 to 1: 9.

JP2000-143941 JP 10-95887

  As described in Patent Document 1, when a thermosetting resin is used as the matrix resin, the resin is cured by heat such as a fire, and the retention of the structure of the refractory sheet composed of the refractory resin composition is good. However, a curing agent must be blended, which may not be preferable in terms of the environment. Moreover, when comprising a fireproof sheet from the fireproof resin composition containing a thermosetting resin, since the fireproof sheet was comprised by press molding or extrusion molding, the temperature at the time of shaping | molding becomes high temperature. For this reason, there has been a restriction that a thermally expandable graphite having a high expansion start temperature such as 200 ° C. or higher must be used so that the thermally expandable graphite does not begin to expand during molding.

  In addition, as described in Patent Document 2, when the fireproof sheet is formed from the fireproof resin composition, the fireproof sheet is also formed by press molding or extrusion molding, so that the temperature is higher than the molding temperature of the thermoplastic resin. There was a restriction that a thermally expandable graphite having a high expansion start temperature had to be used.

  If a refractory sheet is produced by a coating method instead of molding, it can be used even in thermally expandable graphite having a low shrinkage and a low expansion start temperature compared to the molding method with the conventional extrusion molding. In the case of coating, if an organic solvent that dissolves the resin remains, there is a problem of odor or flammability, and depending on the type of the remaining solvent, there is a highly toxic one. Further, when the organic solvent volatilizes, bubbles may be generated in the refractory resin composition, which is not desirable in terms of quality such as appearance.

An object of the present invention is to provide a fire resistant resin composition that is excellent in fire resistance and that reduces or eliminates one or more of the above problems due to the inclusion of the organic solvent as described above in the application of fire prevention equipment. There is.

  The inventors of the present invention have excellent fire resistance and reduce odor and the like by not containing or evaporating an organic solvent when forming a thermally expandable fire resistant sheet from a fire resistant resin composition by coating. It has been found that a thermally expandable fireproof sheet can be produced, and the present invention has been completed.

That is, the present invention encompasses the subject matters described in the following sections.
Item 1. A heat-expandable fireproof sheet containing a thermoplastic resin and heat-expandable graphite, which contains one or more organic solvents, and each organic solvent has a content of 0.01% by mass or less. Inflatable fireproof sheet.
Item 2. Item 2. The thermally expandable refractory sheet according to Item 1, wherein the total content of the organic solvent is 0.01% by mass or less.
Item 3. Item 3. The thermally expandable refractory sheet according to Item 1 or 2, wherein the content of the organic solvent is 5 × 10 ⁻⁶ mass% or less.
Item 4. Item 4. The thermally expandable refractory sheet according to any one of Items 1 to 3, wherein an ignition point of the organic solvent is equal to or higher than an expansion start temperature of the thermally expandable graphite.
Item 5. Item 5. The thermally expandable refractory sheet according to any one of Items 1 to 4, wherein an expansion start temperature of the thermally expandable graphite is 220 ° C or lower.
Item 6. The thermally expandable refractory sheet according to any one of Items 1 to 5, comprising 10 to 350 parts by mass of the thermally expandable graphite with respect to 100 parts by mass of the thermoplastic resin.
Item 7. Item 7. The thermally expandable refractory sheet according to any one of Items 1 to 6, wherein the thermoplastic resin is a polyvinyl chloride resin.
Item 8. Item 8. The thermally expandable refractory sheet according to any one of Items 1 to 7, further comprising 30 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin.

  ADVANTAGE OF THE INVENTION According to this invention, the refractory resin composition which expands from the temperature lower than before, and exhibits fireproof performance and a thermally expansible fireproof sheet can be provided. Moreover, the influence of the odor etc. by containing an organic solvent is also reduced.

  First, the fire resistant resin composition constituting the thermally expandable fire resistant sheet of the present invention will be described.

  The fire resistant resin composition contains a thermoplastic resin and thermally expandable graphite, and the content of the organic solvent in the thermally expandable fire resistant sheet is 0.01% by mass or less.

  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, acrylic resin, polyamide resin, polyvinyl chloride resin, phenol resin, polyurethane resin, and polyisobutylene.

  One or two or more of these thermoplastic resins can be used.

Among these thermoplastic resins, a polyvinyl chloride resin is preferable from the viewpoint of increasing the flame retardancy of the resin itself and improving the fire resistance. The polyvinyl chloride resin includes (1) a vinyl chloride homopolymer, or (2) a copolymer of monomers having an unsaturated bond copolymerizable with vinyl chloride and vinyl chloride, and A vinyl chloride copolymer containing 50% by mass or more of vinyl chloride can be used. The vinyl chloride may be chlorinated vinyl chloride.

  Examples of monomers having an unsaturated bond copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid and methacrylic acid; acrylic acid esters such as methyl acrylate and ethyl acrylate; Examples thereof include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; olefins such as ethylene and propylene; acrylonitrile; aromatic vinyl such as styrene; vinylidene chloride and the like. The average degree of polymerization of the polyvinyl chloride resin used in the present invention is not particularly limited, but is preferably 400 to 3,000, and more preferably 1,000 to 2,000.

  Further, the thermoplastic resin is preferably excellent in solvent solubility from the viewpoint of coatability (productivity). In particular, a polyvinyl chloride resin having a small primary particle size and a spherical shape and a small plasticizer absorption at room temperature, which is a temperature at the time of coating, is particularly preferable.

Furthermore, in this invention, the viscosity in normal temperature can be reduced and the polyvinyl chloride paste resin which can be made into a sheet | seat by heating can also be used. As the polyvinyl chloride paste resin, PSM-176 (trade name) manufactured by Kaneka Corporation, Leuron paste (860) manufactured by Tosoh Corporation, or the like can be used.
Moreover, it is preferable to add a copolymer of vinyl acetate and vinyl chloride to the polyvinyl chloride paste resin as necessary. By adding a copolymer of vinyl acetate and vinyl chloride to a polyvinyl chloride paste resin, the gelation temperature can be lowered, and adverse effects on the thermally expandable graphite during molding can be reduced. Such a resin containing vinyl chloride and vinyl acetate as monomers is also referred to as “vinyl acetate-vinyl chloride resin”.

  Thermally expandable graphite is a conventionally known substance, and a powder such as natural scaly graphite, pyrolytic graphite, quiche graphite, etc. is treated with an inorganic acid such as concentrated sulfuric acid, nitric acid, selenic acid, and a strong oxidizing agent to produce graphite. An intercalation compound is produced, and is a kind of crystalline compound that maintains the layered structure of carbon. Examples of the strong oxidizing agent include concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, dichromate, hydrogen peroxide, and the like.

  The heat-expandable graphite obtained by acid treatment as described above is preferably 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. If the particle size is smaller than 200 mesh, the degree of expansion of graphite is small, and a sufficient expanded heat insulating layer cannot be obtained. If the particle size is larger than 20 mesh, there is an advantage that the degree of expansion of graphite is large. At the same time, dispersibility deteriorates and physical properties deteriorate.

The expansion start temperature of the thermally expandable graphite of the present invention is not particularly limited, but is preferably 220 ° C. or less, more preferably less than 180 ° C., further preferably 170 ° C. or less, and most preferably 160 ° C. or less. is there. As the thermally expandable graphite having an expansion start temperature of less than 180 ° C., a commercially available one is available, and examples thereof include ADT501 from ADT. Since the expansion start temperature of the heat-expandable graphite is less than 180 ° C., the fire-resistant resin composition and the heat-expandable fire-resistant sheet can start expansion at a lower temperature than before. In addition, a heat-expandable fire-resistant sheet can be produced from a fire-resistant resin composition by other methods such as coating that does not require high-temperature molding such as press molding and extrusion molding. The manufacturing variations of can be expanded.
The expansion start temperature of the thermally expandable graphite is measured by measuring the temperature at which the force in the normal direction rises by raising the temperature of the thermally expandable graphite at a constant temperature with a temperature adjustment function and a device that measures the force in the normal direction. It is measurable by doing. For example, a rheometer (TA Instruments Inc. Disco
The above measurement is possible using very HR-2).

  If the content of the heat-expandable graphite is small, sufficient thermal expansibility cannot be obtained, and if it is large, the mechanical properties are greatly deteriorated and cannot be used, so 10 to 350 parts per 100 parts by weight of the thermoplastic resin. It is preferable that it is a mass part.

  The refractory resin composition may further contain an inorganic filler.

  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 And 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.

  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, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel 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.

  As a particle size of an inorganic filler, 0.5-100 micrometers is preferable, More preferably, it is 1-50 micrometers. When the addition amount of the inorganic filler is small, the dispersibility largely affects the performance, so that the particle size is preferably small. However, when it is less than 0.5 μm, secondary aggregation occurs and the dispersibility deteriorates. When the addition amount is large, the viscosity of the resin composition increases and moldability decreases as the high filling progresses, but the viscosity of the resin composition can be decreased by increasing the particle size. A thing with a large diameter is preferable. When the particle size exceeds 100 μm, the surface properties of the molded body and the mechanical properties of the resin composition are lowered.

  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.

  If the content of the inorganic filler is small, sufficient fire resistance performance cannot be obtained, and if it is large, the mechanical properties are greatly deteriorated and cannot be used, so 30 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin. What is contained in the range of is preferable. Moreover, the total of the said thermally expansible graphite and the said inorganic filler has the preferable range of 50-600 mass parts with respect to 100 mass parts of thermoplastic resins.

According to this composition, the heat-expandable resin composition and the heat-expandable fire-resistant sheet formed from the fire-resistant resin composition can be expanded by heating such as a fire to obtain a necessary volume expansion coefficient. A residue having a predetermined heat insulating performance and a predetermined strength can be formed, and a stable fireproof performance can be achieved.

  The refractory resin composition may further contain a phosphorus compound in addition to the components described above.

  As for the phosphorus compound, the thermally expandable resin composition constituting the thermally expandable fireproof sheet increases the strength of the expanded heat insulating layer and improves 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. Among these, from the viewpoint of fire prevention performance, red phosphorus, ammonium polyphosphates, and compounds represented by the following chemical formula (1) are preferable, and ammonium phosphates are more preferable in terms of performance, safety, cost, and the like. .

In the chemical formula (1), R ¹ and R ³ are the same or different and each represents 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 shown.

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, and “FR” manufactured by Budenheim Iberica.
CROS 484 "," FR CROS 487 ", etc. are mentioned.

  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.

The total amount of the phosphorus compound and the thermally expandable graphite is preferably 20 to 200 parts by mass. When it is 20 parts by mass or more, sufficient fire resistance is obtained, and when it is 200 parts by mass or less, mechanical properties are good.

  When the thermoplastic resin is a polyvinyl chloride resin, the refractory resin composition preferably contains a plasticizer in addition to the above components.

Examples of plasticizers include phthalic acid derivatives (particularly phthalic acid esters), trimellitic acid derivatives (particularly trimellitic acid esters), adipic acid derivatives (particularly adipic acid esters), azelaic acid derivatives (particularly azelaic acid). Esters), sebacic acid derivatives (especially sebacic acid esters), sulfonic acid derivatives (especially sulfonic acid esters), epoxy derivatives (especially epoxidized esters), and the like, and polymerization types of dicarboxylic acids and dihydric alcohols A polyester plasticizer that is an ester can be used. Examples of the dicarboxylic acid include adipic acid, azelaic acid, sebacic acid, and phthalic acid. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butylene glycol and the like.
Examples of phthalic acid derivatives (particularly phthalic acid esters) include bis (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, mixed phthalic acid esters of higher alcohols, and the like.
Examples of trimellitic acid derivatives (particularly trimellitic ester) include tris (2-ethylhexyl) trimellitate, tri (n-octyl) trimellitate, triisooctyl trimellitate and the like.
Examples of adipic acid derivatives (particularly adipic acid esters) include bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, and mixed adipic acid esters of higher alcohols.
Examples of azelaic acid derivatives (particularly azelaic acid esters) include bis (2-ethylhexyl) azelate, diisooctylazelate, and di- (n-hexyl) azelate.
Examples of sebacic acid derivatives (particularly sebacic acid esters) include bis (2-ethylhexyl) sebacate and diisooctyl sebacate.
Examples of sulfonic acid derivatives (particularly sulfonic acid esters) include phenolic alkyl sulfonic acid esters.
Epoxy derivatives (particularly epoxidized esters) include epoxidized soybean oil, epoxidized linseed oil, and the like.
Among these plasticizers, a high molecular weight plasticizer is preferable from the viewpoints of migration, extractability, bleeding, and the like. In addition, a plasticizer may be used individually by 1 type, or may use 2 or more types together.

  The content of the plasticizer is preferably 10 to 100 parts by mass and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. Moreover, 40-120 mass parts may be sufficient with respect to 100 mass parts of polyvinyl chloride resin, and 60-105 mass parts may be sufficient as content of a plasticizer. When the content is 10 parts by mass or more, the moldability when forming a sheet-like product becomes a good melt viscosity. On the other hand, when the addition amount is 120 parts by mass or less, it is preferable in terms of maintaining the flame retardancy of the refractory resin composition.

  In addition, the above fire-resistant resin composition does not impair its physical properties, and further, heat stabilizers other than phosphorus compounds, processing aids, pyrolytic foaming agents, phenolic, amine-based, sulfur-based antioxidants, etc. An additive such as an agent, a metal damage preventive agent, an antistatic agent, a stabilizer, a cross-linking agent, a lubricant, a softener, a pigment, a tackifying resin, a tackifier such as polybutene and a petroleum resin, and the like may be added.

  By kneading each component of the refractory resin composition using a known apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a reiki machine, a planetary stirrer, and the like, A resin composition can be obtained.

  A heat-expandable fire-resistant sheet can be produced from the fire-resistant resin composition by, for example, a coating method or a conventionally known molding method such as press molding, extrusion molding, or calendar molding. Preferably, the method for producing a heat-expandable fireproof sheet is formed by coating the fireproof resin composition into a sheet shape to form a coated product, and heating or cooling the coated product. Including solidification. When the coated material contains a polyvinyl chloride resin, the coated material is gelled by heating. Optionally, the coating may be dried after heating or cooling. Drying includes heat drying, pressure drying, and natural drying (that is, drying that does not require heating or pressure). Coating may be performed once or a plurality of times. In addition, the coating may be performed a plurality of times, and the coated product may be stacked into a sheet shape, and then solidified by drying or cooling to produce a thermally expandable refractory sheet, or coating and solidification May be alternately performed a plurality of times to produce a thermally expandable refractory sheet.

  The refractory resin composition is applied to an object to be coated. The article to be coated may be a base material such as a metal plate or a synthetic resin sheet, or a building material for a building. In this specification, “building” includes a building such as a detached house, an apartment house, a high-rise house, a high-rise building, a commercial facility, a public facility; a ship such as a passenger ship, a transport ship, a ferry; a vehicle; Things are included, but not limited to these. In this specification, “building material” refers to any material used to make a building, such as a structure such as a wall, a floor, a brick, a roof, or a plate; a window (a sliding window, a swing window, a raising / lowering window, etc.) ), Shojis, doors (ie doors), bran, and balustrades: wiring, piping; and the like.

The refractory resin composition may or may not contain one or more organic solvents for dissolving the components in the refractory resin composition for coating. Such an organic solvent is not particularly limited. For example, an alcohol organic solvent, a ketone organic solvent, an ester organic solvent, a glycol ester organic solvent, a glycol organic solvent, and the like can be used. From the viewpoint of solubility, glycol ester organic solvents and glycol organic solvents are particularly preferable.
Such an organic solvent is selected according to the type of thermoplastic resin. Specifically, for example, in the case of a polyvinyl chloride resin, tetrahydrofuran (THF, ignition point: 321 ° C.), methyl ethyl ketone (MEK, ignition point: 404). ° C), cyclohexanone (ignition point: 420 ° C), N, N-dimethylformamide (DMF, ignition point: 445 ° C), ethyl carbitol (ignition point: 204 ° C), butyl carbitol (ignition point: 223 ° C), Acetone (ignition point: 465 ° C.), toluene (ignition point: 480 ° C.), methanol (ignition point: 464 ° C.), butyl carbitol acetate (ignition point: 290 ° C.) and the like.
The organic solvent is preferably removed by evaporation from the refractory resin composition by heat drying, vacuum drying, evaporation or the like during the production of the thermally expandable refractory sheet. When the refractory resin composition contains an organic solvent, it is preferable that the amount of the organic solvent is small from the viewpoint of the environment, and the content of each organic solvent in the refractory resin composition is 0.01% by mass. The total content of each organic solvent in the fireproof resin composition is more preferably 0.01% by mass or less. Further, the content of each organic solvent in the thermally expandable fireproof sheet formed from such a fireproof resin composition is also preferably 0.01% by mass or less, respectively, and the total content of each organic solvent is More preferably, it is 0.01 mass% or less.
Thus, one or more problems due to the presence of an organic solvent such as odor, ignition, or bubble generation can be reduced or eliminated. The organic solvent in the refractory resin composition and the thermally expandable refractory sheet is more preferably 5 × 10 ⁻⁴ mass% or less, and more preferably 5 which is the lower limit at which humans can generally feel odor. × 10 ⁻⁶ mass% or less. In this case, there is almost no organic solvent other than the organic solvent unavoidably present in the raw material of the refractory resin composition and the organic solvent unintentionally mixed when the composition is prepared.
Moreover, as an organic solvent, it is preferable that the ignition point is more than the expansion start temperature of thermally expansible graphite. By using an organic solvent whose ignition point is equal to or higher than the expansion start temperature of the thermally expandable graphite, it is possible to reduce the risk of ignition of fire to other parts by reaching the ignition point after expansion.

  Moreover, it is preferable that there is little content of an organic solvent also regarding the base material and adhesion layer which are laminated | stacked on a thermally expansible fireproof sheet.

The heat-expandable fireproof sheet 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 the heating condition of 50 kW / m ² It is preferable that the volume expansion coefficient (also referred to as expansion ratio) after heating for 30 minutes is 3 to 50 times. If the volume expansion rate is less than 3 times, the expansion volume may not be able to fully fill the burned-out portion of the resin component, and fireproof performance may be reduced. On the other hand, if it exceeds 50 times, the strength of the expansion layer is lowered, and the effect of preventing the penetration of the flame may be lowered. More preferably, the volume expansion coefficient is in the range of 5 to 40 times, and more preferably in the range of 8 to 35 times.

  Although the thickness of a thermally expansible fireproof sheet is not specifically limited, It is preferable that it is 0.5 mm-2.5 mm.

  The refractory resin composition and the thermally expandable refractory sheet of the present invention preferably start expansion at less than 180 ° C., more preferably start at 100 ° C. or more and less than 180 ° C., more preferably 100 ° C. or more and 160 Starts expansion below ℃. The heat-expandable fireproof sheet of the present invention can expand from a low temperature and exhibit fireproof performance. By applying the heat-expandable fireproof sheet of the present invention to a building material of a building, in particular, a gap in a fitting such as a window or a door, it is possible to prevent a flame from entering through the gap during a fire or the like. Can do.

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

[Example 1]
A polyvinyl chloride resin, a plasticizer, a thermally expandable graphite, a phosphorus compound, and a heat stabilizer are mixed in the composition (parts by mass) shown in Table 1, and the coating is carried out to a thickness of 1.5 mm. Gelation was performed at 130 ° C., and the thermally expandable fireproof sheet of Example 1 was produced. The following were used as each component.
Vinyl chloride resin Polyvinyl chloride resin Average polymerization degree is 1,650. Leuron paste 772A (trade name) manufactured by Tosohkai Sou Co., Ltd.
Plasticizer Dioctyl phthalate New Nippon Rika Co., Ltd., Sunsocizer DOP (trade name)
Thermally expandable graphite CA60N (trade name) manufactured by Air Water Co., Ltd. (expansion start temperature: 220 ° C.)
Phosphorus compound Ammonium polyphosphate compound Terrage C-70 (trade name) manufactured by CBC Corporation
Thermal stabilizer Ca-Zn composite stabilizer Mizusawa Chemical Co., Ltd. NT-231

[Examples 2 to 10]
While changing the composition of the refractory resin composition constituting the thermally expandable refractory sheet to the composition shown in Table 1, for Examples 4 to 7, Example 1 except that the following thermally expandable graphite was used. A thermally expandable refractory sheet was produced in the same manner as described above.
Note that EXP50S160 (expansion start temperature 160 ° C.) manufactured by Fuji Graphite Industry Co., Ltd. is used as the thermally expandable graphite of Example 4, and EXP50S180 (Fuji Graphite Industry Co., Ltd.) is used as the thermally expandable graphite of Example 5. (Expansion start temperature: 180 ° C.) EXP50S200 (expansion start temperature: 200 ° C.) manufactured by Fuji Graphite Industry Co., Ltd. as the thermally expandable graphite of Example 6, and ADT manufactured as the thermally expandable graphite of Example 7 ADT501 (expansion start temperature 150 ° C.) was used.

[Comparative Example 1]
A polyvinyl chloride resin, a plasticizer, a thermally expandable graphite, a phosphorus compound, and a heat stabilizer are mixed in the composition (parts by mass) shown in Table 1, and coated to a thickness of 1.5 mm. After drying, the thermally expandable fireproof sheet of Comparative Example 1 was produced. The following were used as each component.
Vinyl chloride resin Polyvinyl chloride resin Average polymerization degree 1,650 Tosoh Corporation, Leuron paste 772A (trade name)
Plasticizer Dioctyl phthalate New Nippon Rika Co., Ltd., Sunsocizer DOP (trade name)
Thermally expandable graphite CA60N (trade name) manufactured by Air Water Co., Ltd. (expansion start temperature: 220 ° C.)
Phosphorus compound Ammonium polyphosphate compound Terrage C-70 (trade name) manufactured by CBC Corporation
Heat stabilizer Ca-Zn composite stabilizer Mizusawa Chemical Co., Ltd. NT-231

[Comparative Example 2]
A polyvinyl chloride resin, a plasticizer, a thermally expandable graphite, a phosphorus compound, and a heat stabilizer are mixed in the composition (parts by mass) shown in Table 1, and butyl carbitol as a solvent is 1% of the total weight and acetone is 4%. % Was applied to a thickness of 1.5 mm, dried at 200 ° C., and a thermally expandable fireproof sheet of Comparative Example 2 was produced. The following were used as each component.
Vinyl chloride resin Polyvinyl chloride resin Average polymerization degree 1,650 Tosoh Corporation, Leuron paste 772A (trade name)
Plasticizer Dioctyl phthalate New Nippon Rika Co., Ltd., Sunsocizer DOP (trade name)
Thermally expandable graphite CA60N (trade name) manufactured by Air Water Co., Ltd. (expansion start temperature: 220 ° C.)
Phosphorus compound Ammonium polyphosphate compound Terrage C-70 (trade name) manufactured by CBC Corporation
Heat stabilizer Ca-Zn composite stabilizer Mizusawa Chemical Co., Ltd. NT-231

(Measurement of organic solvent amount)
In order to identify the residual solvent in the sample, it was measured by thermal desorption GC / MS under the following conditions.
<Thermal desorption GC / MS measurement conditions>
Thermal desorption equipment: TurboMatrix 650 (Perkin Elmer)
Sample amount: (1) Approximately 10 mg (2) Sheet approximately 30 mg Precision weighing Heating: 150 ° C, 5 minutes (20 mL / min)
Secondary desorption: 350 ° C, 40 minutes Split: Inlet 20 mL / min Outlet 20 mL / min Injection rate 3.5%
GC / MS system: JMS Q1000GC (JEOL)
Column: EQUITY-1 (Non-polar) 0.32mm x 60m x 0.25μm
GC temperature rise: 40 ° C (4 minutes) → 10 ° C / minute → 100 ° C (10 minutes) → 40 ° C / minute → 300 ° C (2 minutes)
He flow rate: 1.5mL / min Ionization voltage: 70eV
MS measurement range: 29-600amu (scan 500ms)
MS temperature: ion source; 230 ° C, interface; 250 ° C

Next, in order to quantify the solvent confirmed as a result of the thermal desorption GC / MS measurement, a calibration curve was first prepared for the confirmed solvent. A sample to be evaluated was prepared in an approximately 5 wt% chloroform solution, shaken for 3 hours and then filtered, and the filtrate was subjected to GC / MS measurement under the following conditions. Further, GC / MS measurement was similarly performed on 0.1, 0.2, 0.5, 1, 5, and 10 μg / ml chloroform solutions of each standard sample for preparing a calibration curve.
<GC / MS measurement conditions>
Equipment: JMS-Q1500 (JEOL)
GC column: SLBTM-5ms (slight polarity) 0.25mm x 30m x 0.25μm
Inlet temperature: 300 ° C
Injection volume: 1μL
GC temperature rise: 40 ° C (4 minutes) → 10 ° C / minute → 300 ° C (0 minutes)
He flow rate: 1.0 ml / min split ratio 1:50
MS measurement range: 29-600
Ionization voltage: 70eV
MS temperature: ion source; 230 ° C, interface; 250 ° C
The amount of organic solvent was measured from the obtained measurement data and calibration curve.
(Heating test)
Each thermally expansible refractory sheet of an example and a comparative example was heated for 30 minutes at 600 ° C, and change of thickness (volume expansion coefficient) was measured. The results are shown in Table 1.

  The heat-expandable fireproof sheet of the example has a good volume expansion coefficient. Further, the amount of organic solvent was not more than the specified amount from the thermally expandable refractory sheet of each example.

  While the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications based on the technical idea of the present invention are possible.

  The configurations, methods, steps, shapes, materials, numerical values, and the like of the above-described embodiments can be combined with each other without departing from the gist of the present invention.

Claims (8)

A thermally expandable refractory sheet containing a thermoplastic resin and thermally expandable graphite,
A thermally expandable refractory sheet containing one or two or more organic solvents, wherein the content of each organic solvent is 0.01% by mass or less.   The thermally expandable refractory sheet according to claim 1, wherein the total content of the organic solvent is 0.01% by mass or less. The thermally expandable refractory sheet according to claim 1 or 2, wherein the content of the organic solvent is 5 x ^10-6 mass% or less.   4. The thermally expandable refractory sheet according to claim 1, wherein an ignition point of the organic solvent is equal to or higher than an expansion start temperature of the thermally expandable graphite.   The expansion start temperature of the said thermally expansible graphite is 220 degrees C or less, The thermally expansible fireproof sheet as described in any one of Claims 1-4.   The thermally expandable refractory sheet according to any one of claims 1 to 5, comprising 10 to 350 parts by mass of the thermally expandable graphite with respect to 100 parts by mass of the thermoplastic resin.   The thermally expandable refractory sheet according to any one of claims 1 to 6, wherein the thermoplastic resin is a polyvinyl chloride resin.   The thermally expandable refractory sheet according to any one of claims 1 to 7, further comprising 30 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin.