JP6159463B1 - Fireproof resin composition - Google Patents

Abstract

An object of the present invention is to provide a fire-resistant resin composition having excellent flame retardancy, surface finish and strength. In a refractory resin composition containing a matrix component which is a resin, elastomer, rubber, or a combination thereof, thermally expandable graphite, and an inorganic filler, the particle shape of the inorganic filler is spherical. A fire resistant resin composition. [Selection figure] None

Description

  The present invention relates to a refractory resin composition.

  Resin materials containing thermally expandable graphite have been proposed as resin materials imparted with fire resistance used in the construction field (Patent Documents 1 to 4).

  However, a refractory material containing thermally expandable graphite must be shortened in processing time because the components in the thermally expandable graphite are lost unless the processing time is shortened, and the expansion ratio is reduced. On the other hand, refractory materials often contain a large amount of inorganic fillers and flame retardant materials in combination with thermally expandable graphite. In some cases, the refractory material becomes brittle, the surface becomes dirty (powder is blown / black), and handling is hindered.

JP-A-9-227716 JP-A-9-227747 JP-A-10-95887 JP 2000-143941 A

  An object of the present invention is to provide a fire-resistant resin composition having excellent flame retardancy, surface finish, and strength.

  In order to achieve the above object, the present inventor has found that the above problem can be solved by using an inorganic filler having a spherical particle shape in the refractory resin composition, and has completed the present invention. It was.

  The present invention includes the following aspects.

Item 1. In a refractory resin composition containing a matrix component that is a resin, elastomer, rubber, or a combination thereof, thermally expandable graphite, and an inorganic filler,
A fire resistant resin composition comprising an inorganic filler having a spherical particle shape.

Item 2. Item 2. Item 1, wherein the total content of thermally expandable graphite and the spherical inorganic filler is 30% by weight or more, and the content of thermally expandable graphite is 15% by weight or more. Item 3. Fire-resistant resin composition Item 3. The fireproof resin composition according to Item 1 or 2, wherein the inorganic filler contains phosphite.

  Item 4. Item 4. The fireproof resin composition according to any one of Items 1 to 3, further comprising a polyphosphate.

Item 5. Item 5. The fireproof resin composition according to any one of Items 1 to 4, wherein the ratio of the aspect ratio of the thermally expandable graphite to the aspect ratio of the inorganic filler is 2 or more.

  Item 6. Item 6. The fireproof resin composition according to any one of Items 1 to 5, further comprising a plasticizer.

  Item 7. Item 7. The fire resistant resin composition according to any one of Items 1 to 6, wherein the matrix component is a vinyl chloride resin or a polyolefin resin.

  Item 8. Item 8. A fire-resistant resin molded article comprising the fire-resistant resin composition according to any one of items 1 to 7.

  Item 9. A joinery comprising the fireproof resin molded article according to Item 8.

  ADVANTAGE OF THE INVENTION According to this invention, the fireproof resin composition which is excellent in a flame retardance, and is excellent in surface finish and intensity | strength is provided.

It is a schematic front view which shows the fireproof window which provided the fireproof resin molding which consists of a fireproof resin composition of this invention in the sash frame.

  Embodiments of the present invention will be described below.

  The matrix component may be any of resin, elastomer, and rubber. The resin includes a thermoplastic resin and a thermosetting resin.

  Examples of the thermoplastic resin include polypropylene resin, polyethylene resin, poly (1-) butene resin, polypentene resin, ethylene-propylene copolymer, ethylene-butene copolymer resin, and ethylene-4-methyl-1-pentene copolymer. Polyolefin resin such as polymer resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene-acrylic acid copolymer; polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate resin, polyphenylene ether resin, (meta ) Synthetic resins such as acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), chlorinated polyvinyl chloride resin (CPVC), novolac resin, polyurethane resin, polyisobutylene.

  Any of the above thermoplastic resins may be used after being crosslinked or modified within a range not impairing the fire resistance performance of the resin composition. The crosslinking method of the resin is not particularly limited, and examples thereof include a usual crosslinking method for thermoplastic resins, such as crosslinking using various crosslinking agents and peroxides, and crosslinking by electron beam irradiation.

  Examples of the thermosetting resin include synthetic resins such as polyurethane, polyisocyanate, polyisocyanurate, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide. Among these, an epoxy resin is preferable.

  The epoxy resin used in the present invention is not particularly limited, but is basically obtained by reacting a monomer having an epoxy group with a curing agent. Examples of the monomer having an epoxy group include monomers such as a bifunctional glycidyl ether type, a glycidyl ester type, and a polyfunctional glycidyl ether type.

These monomers having an epoxy group may be used alone or in combination of two or more.

  As the curing agent, a polyaddition type or a catalyst type is used. Examples of the polyaddition type curing agent include polyamine, acid anhydride, polyphenol, and polymercaptan. Examples of the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes. The curing method of the epoxy resin is not particularly limited, and can be performed by a known method.

  Examples of elastomers include olefin elastomers (TPO), styrene elastomers, ester elastomers, amide elastomers, vinyl chloride elastomers, combinations thereof, and the like.

  Rubber materials include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, ethylene-propylene diene rubber (EPDM). ), Rubber materials such as chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicon rubber, fluorine rubber, and urethane rubber. Of these, butyl rubber is preferred.

  These synthetic resins and / or rubber substances can be used singly or in combination.

  Among these synthetic resins and / or rubber substances, polyvinyl chloride resins such as polyvinyl chloride resins and chlorinated polyvinyl chloride resins are preferable from the viewpoint that they can contain many plasticizers and have excellent kneading efficiency. . Further, from the viewpoint of excellent processability and economic efficiency, polyolefin resins such as ethylene-vinyl acetate copolymer resin (EVA) are also preferable.

  Thermally expandable graphite is a conventionally known substance and has a characteristic of expanding when heated. Powders such as natural scale graphite, pyrolytic graphite, quiche graphite, inorganic acids such as concentrated sulfuric acid, nitric acid, selenic acid, concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, A graphite intercalation compound is produced by treatment with a strong oxidizing agent such as dichromate or hydrogen peroxide, and is a kind of crystalline compound that maintains the layered structure of carbon.

  The heat-expandable graphite obtained by acid treatment as described above may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.

  The larger the particle size (particle size) of the thermally expandable graphite, the greater the expansion performance and the better the fire resistance. However, the larger the particle size, the more difficult it is to disperse in the matrix, and the time for kneading is required. From the viewpoint of the expansion ratio, the particle size of the thermally expandable graphite is preferably 100 μm or more, more preferably 400 μm or more. The upper limit of the particle size of the thermally expandable graphite is not particularly limited, but is preferably 1500 μm or less, and more preferably 1000 μm or less. Since the particle size is reflected in the particle size of the graphite used, it can be controlled by using a commercially available thermally expandable graphite classified by a predetermined sieve. The average particle size was defined as the particle size of 50% of the accumulated amount from the small particle size side of the raw material used. Alternatively, the cross-sectional SEM (scanning electron microscope image) of the prepared sheet is observed to determine the particle size distribution of the thermally expandable graphite, and in the volume-based particle size distribution obtained therefrom, the accumulated amount from the small particle size side is 50. % Particle diameter can also be determined as the average particle diameter.

The content of the thermally expandable graphite is not particularly limited, but is preferably 10 to 500 parts by weight with respect to 100 parts by weight of the matrix component, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the matrix component. preferable. When the content is 10 parts by weight or more, a fire expansion performance that sufficiently fills a portion where a structure such as a sash is burned out is exhibited and the mechanical strength is maintained when the content is 500 parts by weight or less.

  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 balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, 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.

  In one embodiment, the inorganic filler is selected from metal oxides, hydrous minerals, metal carbonates, silica, and combinations thereof. The hydrous inorganic substance contains an alkaline earth metal hydroxide.

  As the inorganic filler, a flame retardant compound (a flame retardant) such as a phosphorus compound may be added.

  Addition of the phosphorus compound 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 (TCP), trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate; Examples thereof include metal phosphates such as sodium phosphate, potassium phosphate, and magnesium phosphate; compounds represented by the following chemical formula (1), and the like.

In the chemical formula (1), R ¹ and R ³ , hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms is represented. R ² is a hydroxyl group having 1 to 16 carbon atoms.
A linear or branched alkyl group, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or an aryloxy group having 6 to 16 carbon atoms.

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 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.

  Alternatively, it may be a salt of lower phosphoric acid such as primary phosphoric acid, secondary phosphoric acid, tertiary phosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, or the like. In this specification, a salt includes alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; other metal salts such as aluminum salt; ammonium salt and the like.

  In the composition of the present invention, the inorganic filler contains spherical particles. A spherical shape means an aspect ratio of 2 or less, particularly 1.5 or less. The aspect ratio represents the ratio of the major axis to the minor axis of the particle.

  The spherical shape may be a true spherical shape, an elliptical shape obtained by flattening a sphere, or a shape similar to these. For example, when the particle shape is a random shape, a cubic shape, a spindle shape, a fiber shape, or the like, it is understood that the shape is not spherical.

  The aspect ratio can be determined, for example, by measurement using a digital image analysis system particle size distribution measuring apparatus (trade name: FPA, manufactured by Nippon Luft).

  Although not restricting the present invention, it is presumed that the spherical inorganic filler particles are efficiently arranged between the thermally expandable graphite particles and the effects of the present invention are exhibited.

  As a particle size of an inorganic filler, 0.5-200 micrometers is preferable, More preferably, it is 1-10 micrometers. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance, so that the particle size is preferably small, but if it is 0.5 μm or more, the dispersibility is good. When the addition amount is large, the viscosity of the 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. Although a thing with a large diameter is preferable, the particle size of 100 micrometers or less is desirable at the point of the surface property of a molded object, and the mechanical physical property of a resin composition. The average particle size was defined as the particle size of 50% of the accumulated amount from the small particle size side of the raw material used. Further, the cross-sectional SEM (scanning electron microscope image) of the prepared sheet is observed to determine the particle size distribution of the inorganic filler. In the volume-based particle size distribution obtained therefrom, the accumulated amount from the small particle size side is 50%. The particle diameter can be the average particle diameter.

  Further, in order to make the aggregated raw material into spherical particles, it is possible to carry out a treatment such as charging the aggregated inorganic filler after being broken or dispersed in a solvent.

Examples of the inorganic filler having a spherical particle shape include glass beads “UBS having a particle diameter of 30 μm”.
-0030L "(manufactured by Unitika Ltd.)," MSR-2212 "(Tatsumori Co., Ltd.) with a particle size of 25.5 µm for silica, and" DAM-70 "(manufactured by Denki Kagaku Kogyo Co., Ltd.) with a particle size of 40 µm for aluminum oxide ,
Examples thereof include aluminum phosphite “APA100” 50 μm (produced by Taihei Chemical Co., Ltd.).

  Although content of an inorganic filler is not specifically limited, It is preferable that it is 30-500 weight part with respect to 100 weight part of matrix components. When the content is 30 parts by weight or more, sufficient fireproof performance is obtained, and when it is 500 parts by weight or less, the mechanical strength is maintained. The content of the inorganic filler is more preferably 40 to 350 parts by weight.

  When the phosphorus compound is contained as the inorganic filler, the content of the phosphorus compound is not particularly limited, but is preferably 30 to 300 parts by weight with respect to 100 parts by weight of the matrix component. When the blending amount is 30 parts by weight or more, the effect of improving the strength of the expanded heat insulating layer is sufficient, and when it is 300 parts by weight or less, the mechanical strength is maintained. The content of the phosphorus compound is more preferably 40 to 250 parts by weight.

In one preferred embodiment of the refractory resin composition of the present invention, the particle size ratio (graphite / inorganic) between the particle size of the thermally expandable graphite and the particle size of the inorganic filler is 1-1000. Preferably 3 to 500,
More preferably, it is 5-50. By setting it as such a numerical range, it can knead | mix efficiently in a short time. On the other hand, if the particle size ratio is out of the above range, dispersion of the heat-expandable graphite in the matrix is insufficient and problems such as surface contamination occur.

  In one preferred embodiment of the refractory resin composition of the present invention, the total content of thermally expandable graphite and spherical inorganic filler is 30% by weight or more. Preferably it is 50 weight% or more. The upper limit of the total content of the thermally expandable graphite and the inorganic filler is not particularly limited, but is 75% by weight or less, preferably 60% or less. By setting it as such a numerical value range, the outstanding fire resistance can be expressed.

  In one preferred embodiment of the refractory resin composition of the present invention, the content of thermally expandable graphite is 15% by weight or more, preferably 20% by weight or more, more preferably 25% by weight or more. . The upper limit of the content of the heat-expandable graphite is not particularly limited, but is 75% by weight or less and 50% by weight or less. By setting it as such a numerical value range, the outstanding fire resistance can be expressed.

  The fireproof resin composition of the present invention may further contain a polyphosphate. The polyphosphate functions as a flame retardant and includes ammonium polyphosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, and the like. Commercially available products of ammonium polyphosphate include “AP422” and “AP462” manufactured by Clariant, “Sumisafe P” manufactured by Sumitomo Chemical Co., Ltd., and “Terrage C60” manufactured by Chisso.

A preferred ammonium polyphosphate is a surface-coated ammonium polyphosphate (also referred to as a coated ammonium polyphosphate). Of the coated ammonium polyphosphates, melamine-coated ammonium polyphosphate surface-coated with melamine is disclosed in JP-A-9-286875. JP-A-2000-63562 describes a silane-coated ammonium polyphosphate surface-coated with silane. The melamine-coated ammonium polyphosphate is composed of (a) melamine-coated ammonium polyphosphate obtained by adding and / or adhering melamine to the surface of powdered ammonium polyphosphate particles, and (b) melamine molecules present in the coating layer of the melamine-coated ammonium polyphosphate particles. And / or (c) powdered ammonium polyphosphate or the melamine in which the particle surface is crosslinked with an active hydrogen possessed by an amino group therein and a compound having a functional group capable of reacting with the active hydrogen This is a coated ammonium polyphosphate in which the surface of the coated ammonium polyphosphate particles is coated with a thermosetting resin. Commercially available melamine-coated ammonium polyphosphate particles include, for example, “AP462” manufactured by Clariant, “FR CROS 484” manufactured by Budenheim Iberica, and “FR”.
CROS 487 "and the like. Examples of commercially available silane-coated ammonium polyphosphate particles include “FR CROS 486” manufactured by Budenheim Iberica.

  The average particle diameter of the coated ammonium polyphosphate is preferably 15 to 35 μm. The average particle diameter of the coated ammonium polyphosphate can be measured by laser diffraction particle size distribution measurement.

  The fireproof resin composition of the present invention may further contain a plasticizer.

The plasticizer is added in order to adjust the melt viscosity of the matrix component, particularly the thermoplastic resin. The plasticizer can also be called a softener. As the plasticizer, one or more plasticizers exemplified below may be used in combination:
Di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or a higher or mixed alcohol having about 10 to 13 carbon atoms Phthalate plasticizers such as phthalates
Aliphatic dibasic acids such as di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate Ester plasticizers;
Trimerits such as tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellitate Acid ester plasticizers;
Adipate plasticizers such as di-2-ethylhexyl adipate (DOA) and diisodecyl adipate (DIDA);
Sebacic acid ester plasticizers such as dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate (DOS);
Tributyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate Phosphate ester plasticizers such as tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate;
Biphenyltetracarboxylic acid tetraalkyl ester plasticizers such as 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetraheptyl ester;
Polyester polymer plasticizer;
Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, and liquid epoxy resin;
Chlorinated paraffin;
Chlorinated fatty acid esters such as alkyl pentastearate; and process oils such as paraffinic process oil, naphthenic process oil, and aromatic process oil.

  The content of the plasticizer in the refractory resin composition is not particularly limited, but is preferably in the range of 25 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

  In addition, a heat stabilizer, a lubricant, a processing aid, a pyrolytic foaming agent, an antioxidant, an antistatic agent, a pigment, and the like are added to the fireproof resin composition of the present invention as long as the physical properties are not impaired. May be.

Examples of the heat stabilizer include lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, dibasic lead stearate; organotin mercapto, organic Organotin heat stabilizers such as tin malate, organotin laurate, dibutyltin malate; metal soap heat stabilizers such as zinc stearate and calcium stearate; these may be used alone or in combination of two or more You may use together.

  Examples of the lubricant include waxes such as polyethylene, paraffin, and montanic acid; various ester waxes; organic acids such as stearic acid and ricinoleic acid; organic alcohols such as stearyl alcohol; and amide compounds such as dimethylbisamide. These may be used alone or in combination of two or more.

  Examples of the processing aid include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, and high molecular weight polymethyl methacrylate.

  Examples of the pyrolytic foaming agent include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), p, p-oxybisbenzenesulfonylhydrazide (OBSH), azobisisobutyronitrile (AIBN), and the like. Can be mentioned.

  The fire-resistant resin composition of the present invention can be obtained by a melt-extrusion using an extruder such as a single screw extruder or a twin screw extruder according to a conventional method. The melting temperature varies depending on the matrix component and is not particularly limited. For example, in the case of a polyvinyl chloride resin, the melting temperature is 130 to 170 ° C.

  The fire-resistant resin composition or fire-resistant resin molded article of the present invention is intended to impart fire resistance to structures such as windows, shojis, doors (ie, doors), doors, brans, and bams; ships; and elevators and other structures. Can be used. Since the fireproof resin composition of the present invention is excellent in moldability, it is possible to easily obtain a modified molded body adapted to the complicated shape of the structure. FIG. 1 is an example in which a fireproof resin molded body 4 of the present invention is applied to a sash frame of a window 1 as a fitting. In this example, the sash frame has two inner frames 2 and one outer frame 3 surrounding the inner frame 2, and the inner frame 2 and the outer frame 3 along each side of the frame main body 2. And the fireproof resin molding 3 is attached to the inside of the outer frame 3. Thus, fire resistance can be imparted to the window 1 by providing the fireproof resin molded body 3 of the present invention.

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

1. Preparation of fireproof sheet [Example 1]
In the blending amounts shown in Table 1, 100 parts by weight of polyvinyl chloride as a synthetic resin (matrix component), 80 parts by weight of diisodecyl phthalate (DIDP) as a plasticizer, thermally expandable graphite (“GREP-EG” manufactured by Tosoh Corporation, granules (Diameter: 800 μm) 100 parts by weight and 50 parts by weight of aluminum phosphite (particle shape: spherical) as an inorganic filler were mixed in a kneader, and the mixture was molded into a sheet shape with a calender roll, 1.5 mm A fireproof sheet as a fireproof resin molding was obtained. In addition, the constant temperature bath temperature in a kneader was 130 ° C., the kneading time was 5 minutes after adding graphite, and the rotation speed was unified to 30 rpm.

[Examples 2 to 15 and Comparative Examples 1 to 4]
For Examples 2 to 15 and Comparative Examples 1 to 4, the components were mixed and extruded at the blending amounts shown in Tables 1 to 3 to obtain fireproof sheets.

The details of each component in the table are as follows.

・ Synthetic resin (matrix component)
Polyvinyl chloride resin (PVC): “TK-1000” manufactured by Shin-Etsu Chemical Co., Ltd.
Chlorinated polyvinyl chloride resin (CPVC): “HA-53F” manufactured by Tokuyama Sekisui Industry Co., Ltd.
Ethylene-vinyl acetate copolymer resin (EVA): “EV460” manufactured by Mitsui DuPont Polychemical Co., Ltd.
Ethylene-propylene-diene rubber (EPDM): “EPT3092M” manufactured by Mitsui Chemicals, Inc.
Olefin-based thermoplastic elastomer (TPO): “Milastomer” manufactured by Mitsui Chemicals, Inc.

Inorganic filler Alumina (spherical): “DAM-45” manufactured by Denka Co., Ltd.
Silica (spherical): “FB-950” manufactured by Denka Co., Ltd.
Ceramic (spherical): Tolsa, Pansil UltraSpheres,
Aluminum nitride (spherical): “Shapal” (50 μm) manufactured by Tokuyama Corporation
Glass (spherical): “DL-7000” manufactured by Nippon Electric Glass Co., Ltd.
Glass beads (spherical): Glass beads manufactured by Nippon Frit Co., Ltd.

2. Evaluation of surface finish of fire-resistant sheet The surface finish of the fire-resistant sheets of Examples 1 to 15 and Comparative Examples 1 to 4 was visually checked for surface roughness (presence of wrinkles and cracks) and dirt (surface exposure of powder). Evaluated by confirmation. The definition of wrinkles and cracks is 3 mm or more, and the exposure of the powder is defined as white on the black sheet surface or the exposed area of graphite is 4 mm 2 or more. In the prepared sheet of width 100 cm × 100 cm, if it was within 5 places, it was rated as ○, and if it was 5 places or more, it was marked as x:
○: No wrinkle on the surface or wrinkles of 3 mm or more within 5 places / m ² ×: Wrinkles of 3 mm or more on the surface are 5 places / m ² or more.

  The fireproof sheets of Examples 1 to 15 were excellent in surface finish, and the deterioration of quality was suppressed.

3. Measurement of expansion ratio A test piece (length 100 mm, width 100 mm, thickness 1.5 mm) prepared from the obtained fireproof sheet was placed in a predetermined holder, supplied to an electric furnace, and heated at 600 ° C. for 30 minutes. The thickness of the test piece was measured, and (thickness of the test piece after heating) / (thickness of the test piece before heating) was calculated as the expansion ratio.

4). Evaluation of Strength The breaking method of the fireproof sheets of Examples 2 to 15 was measured according to JISK7161, and the tensile strength in the flow direction of the roll was measured. Those that were broken when the strain was 110% were marked with ×, and those that were not broken were marked with ○.

Claims (9)

Matrix components in the refractory resin composition containing heat-expandable graphite and an inorganic filler,
The matrix component comprises a thermoplastic resin;
A fire resistant resin composition comprising an inorganic filler having a spherical particle shape. The total content of the heat-expandable graphite and the spherical inorganic filler is 30% by weight or more, and the content of the heat-expandable graphite is 15% by weight or more. Refractory resin composition   The refractory resin composition according to claim 1 or 2, wherein the spherical inorganic filler contains phosphite.   The refractory resin composition according to any one of claims 1 to 3, further comprising a polyphosphate.   The ratio of the aspect ratio of thermally expansible graphite and the aspect ratio of an inorganic filler is 2 or more, The refractory resin composition of any one of Claims 1-4 characterized by the above-mentioned.   The refractory resin composition according to any one of claims 1 to 5, further comprising a plasticizer.   The refractory resin composition according to any one of claims 1 to 6, wherein the matrix component is a vinyl chloride resin or a polyolefin resin.   A fire-resistant resin molded article comprising the fire-resistant resin composition according to any one of claims 1 to 7.   A joinery comprising the fire-resistant resin molded product according to claim 8.