JP2018070879A - Thermally-expandable refractory sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a refractory resin composition that can expand at a lower temperature than before, to exhibit a refractory performance.SOLUTION: A refractory resin composition contains a thermoplastic resin and thermally-expandable graphite with an expansion start temperature of less than 180°C.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 phosphorus compound, neutralized thermally expandable graphite, and an inorganic filler in a polyvinyl chloride resin, each content being 100 wt.% Of the polyvinyl chloride resin. The total amount of the phosphorus compound and neutralized heat-expandable graphite is 20 to 200 parts by weight, the inorganic filler is 30 to 500 parts by weight, and the neutralized heat-expandable graphite: phosphorus compound Is a polyvinyl chloride resin composition characterized by having a weight ratio of 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 mix | blending a hardening | curing agent, when it is going to accelerate | stimulate hardening, hardening may start during production on the relationship of a pot life, and it may become a cause of variation and shaping | molding defect. On the other hand, if the curing is delayed, there is a problem that productivity deteriorates, which is not preferable in terms of production.

  On the other hand, as described in Patent Document 2, when the refractory sheet is formed from the refractory resin composition containing the thermoplastic resin, the refractory sheet is formed by press molding or extrusion molding. Becomes hot. 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.

  When the expansion start temperature of the heat-expandable graphite is high, since the expansion does not start until the temperature of the refractory resin composition or the refractory sheet reaches a high temperature, the expression of the fire resistance is delayed.

  An object of the present invention is to provide a refractory resin composition containing a thermoplastic resin that can expand even at low temperatures.

  The present inventors have found that by forming a fireproof sheet from a fireproof resin composition by coating, even when a thermoplastic resin is used as the matrix resin, a thermally expandable graphite having a low expansion start temperature can be blended. The present invention has been completed.

That is, the present invention encompasses the subject matters described in the following sections.
Item 1. A fire resistant resin composition comprising a thermoplastic resin and a thermally expandable graphite having an expansion start temperature of less than 180 ° C.
Item 2. Item 2. The fire-resistant resin composition according to Item 1, comprising 10 to 350 parts by mass of the thermally expandable graphite with respect to 100 parts by mass of the thermoplastic resin.
Item 3. Item 3. The fireproof resin composition according to Item 1 or 2, wherein the thermoplastic resin is a polyvinyl chloride resin.
Item 4. Item 4. The fire-resistant resin composition according to any one of Items 1 to 3, wherein the thermoplastic resin contains a vinyl acetate-vinyl chloride resin.
Item 5. Item 5. The fire-resistant resin composition according to any one of Items 1 to 4, comprising 40 to 120 parts by mass of a plasticizer with respect to 100 parts by mass of the thermoplastic resin.
Item 6. Item 6. The fire resistant resin composition according to any one of Items 1 to 5, further comprising 30 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin.
Item 7. The fire-resistant resin composition according to any one of Items 1 to 6, comprising an organic solvent of 0.05% by mass or less.
Item 8. The process of applying the fireproof resin composition as described in any one of claim | item 1 -7, and forming a coated material,
The manufacturing method of the thermally expansible fireproof sheet | seat including the process which makes the said coated material gelatinize or solidifies the said coated material by cooling.
Item 9. Item 9. The manufacturing method according to Item 8, wherein the coating is performed a plurality of times and the coated products are stacked to form a sheet shape.

  According to the present invention, since thermally expandable graphite having a lower expansion start temperature than conventional can be blended in the refractory resin composition, a refractory resin composition that expands from a temperature lower than conventional and exhibits fire resistance performance, and A fire resistant resin composition can be provided.

  The fire resistant resin composition of the present invention contains a thermoplastic resin and a thermally expandable graphite having an expansion start temperature of less than 180 ° C.

  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 temperature of the thermally expandable graphite of the present invention is less than 180 ° C., preferably 170 ° C. or less, more preferably 160 ° C. or less. As the thermally expandable graphite having an expansion start temperature of less than 180 ° C., a commercially available one can be obtained, for example, ADT501 manufactured by 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 determined by increasing the temperature of the thermally expandable graphite or the thermally expandable sheet at a constant temperature with a device for measuring the temperature adjustment function and the force in the normal direction. Can be measured by measuring the temperature at which the rises. For example, the above measurement is possible using a rheometer (TA Instruments Discovery 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 of the present invention 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 Metal hydroxides 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 an inorganic filler, for example, in the case of aluminum hydroxide, “Heidilite H-31” (manufactured by Showa Denko KK) having a particle size of 18 μm, “B325” (manufactured by ALCOA) having a particle size of 25 μm, Examples thereof include “Whiteon SB red” having a diameter of 1.8 μm (manufactured by Bihoku Powder Chemical Co., Ltd.), “BF300” having a particle diameter of 8 μm (manufactured by Bihoku Powder Chemical Industries, Ltd.)

  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 fireproof resin composition of the present invention may further contain a phosphorus compound in addition to the above components.

  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, “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.

  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 of the present invention 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 from the viewpoint of maintaining the flame retardancy of the fireproof resin composition.

  In addition, the fireproof resin composition of the present invention includes a heat stabilizer other than a phosphorus compound, a processing aid, a pyrolytic foaming agent, a phenolic, amine-based, sulfur-based, etc., as long as the physical properties are not impaired. Antioxidants, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, additives such as tackifier resins, tackifiers such as polybutene and petroleum resins, etc. 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, 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. By adding a small amount of organic solvent, the viscosity during coating can be reduced. 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.

Preferably, the organic solvent in the heat-expandable fireproof sheet formed from the fireproof resin composition and the fireproof resin composition of the present invention is generally the lower limit at which a human can feel an odor of 5 × 10 ^{−. 6} % by 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 the ratio of the viscosity in 120 degreeC with respect to the viscosity in 50 degreeC is 0.1 or less. The viscosity ratio can be appropriately set by those skilled in the art by adjusting the addition amount and particle size of the inorganic filler or the addition amount of other components. When the viscosity ratio is 0.1 or less, it is possible to ensure productivity during coating production while maintaining the strength during normal use.

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-2.0 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 ° C. Starts expansion below ℃. The heat-expandable fireproof sheet formed from the fireproof resin composition of the present invention can expand from a low temperature and exhibit fireproof performance. By applying the fire-resistant resin composition and the heat-expandable fire-resistant sheet of the present invention to a building material of a building, particularly a gap in a fitting such as a window or a door, a flame penetrates through the gap during a fire or the like. Can be prevented.

  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 coated to a thickness of 1.5 mm, 130 ° C. To produce a thermally expandable fireproof sheet of Example 1. 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 ADT501 made by ADT (trade name)
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

[Examples 2 to 8, 12]
A thermally expandable refractory sheet was produced in the same manner as in Example 1 except that the composition shown in Table 1 was changed. PCH-843 (manufactured by Kaneka Corporation) was used as the vinyl acetate-polyvinyl chloride copolymer. Further, EXP50S160 (trade name) manufactured by Fuji Graphite Industry Co., Ltd. was used as the thermally expandable graphite having an expansion start temperature of 160 ° C.

[Examples 9 to 11]
Thermal expansion was performed in the same manner as in Example 1 except that the composition of the refractory resin composition constituting the thermally expandable refractory sheet was changed to the composition shown in Table 1 and 500 ppm of butyl carbitol was added as an organic solvent. Fireproof sheet was produced.

[Comparative Example 1]
Instead of the thermally expandable graphite of Example 1, SYZR802 (trade name) manufactured by Sanyo Trading Co., Ltd. having an expansion start temperature of 180 ° C. and an average particle diameter of 180 μm was used, and the thermally expandable refractory sheet of Comparative Example 1 was used. Manufactured.

(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)
The heat-expandable refractory sheets of Examples 1 to 12 and Comparative Example 1 were heated at 200 ° C. for 30 minutes, and the change in thickness (volume expansion coefficient) was measured. The results are shown in Table 1.

  Although 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 (9)

  A fire resistant resin composition comprising a thermoplastic resin and a thermally expandable graphite having an expansion start temperature of less than 180 ° C.   The refractory resin composition according to claim 1, comprising 10 to 350 parts by mass of the thermally expandable graphite with respect to 100 parts by mass of the thermoplastic resin.   The fireproof resin composition according to claim 1 or 2, wherein the thermoplastic resin is a polyvinyl chloride resin.   The refractory resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin contains a vinyl acetate-vinyl chloride resin.   The refractory resin composition according to any one of claims 1 to 4, comprising 40 to 120 parts by mass of a plasticizer with respect to 100 parts by mass of the thermoplastic resin.   The refractory resin composition according to any one of claims 1 to 5, further comprising 30 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin.   The fireproof resin composition according to any one of claims 1 to 6, comprising 0.05% by mass or less of an organic solvent. Applying the refractory resin composition according to any one of claims 1 to 7 to form a coated product;
The manufacturing method of the thermally expansible fireproof sheet | seat including the process which makes the said coated material gelatinize or solidifies the said coated material by cooling.   The manufacturing method according to claim 8, wherein the coating is performed a plurality of times, and the coated products are stacked to form a sheet shape.