JP2023115102A - Fire-resistant resin composition - Google Patents

Abstract

To provide a fire-resistant resin composition excellent in flame retardancy and also excellent in surface finish and strength.SOLUTION: The fire-resistant resin composition contains: a matrix component which is a resin, an elastomer, a rubber, or a combination thereof; thermally expandable graphite; and an inorganic filler. The particle diameter ratio of the particle diameter of the thermally expandable graphite to the particle diameter of the inorganic filler is in the range of 1-1,000. The total content of the thermally expandable graphite and the inorganic filler is 30 wt.% or more. The content of the thermally expandable graphite is 5 wt.% or more.SELECTED DRAWING: None

Description

The present invention relates to a fire resistant resin composition.

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

However, in the case of a refractory material containing thermally expandable graphite, if the processing time is not shortened, the components in the thermally expandable graphite will escape and the expansion ratio will decrease, so it is necessary to shorten the processing time. On the other hand, refractory materials often contain a large amount of inorganic fillers and flame retardants as well as thermally expandable graphite. If there is, problems such as the refractory material becoming brittle, the surface becoming dirty (powdering, blackening), and handling being hindered. In addition, the refractory performance may vary depending on the sampling position of the refractory material.

Japanese Patent Laid-Open No. 9-227716 Japanese Patent Laid-Open No. 9-227747 Japanese Patent Laid-Open No. 10-95887 JP 2000-143941

SUMMARY OF THE INVENTION An object of the present invention is to provide a fire-resistant resin composition which is excellent in expandability, stably exhibits performance and fire resistance, and is excellent in surface finish and strength.

In order to achieve the above object, the present inventors have provided a fire-resistant resin composition in which the particle size ratio of the particle size of the thermally expandable graphite and the particle size of the inorganic filler is 1 to 1000, and the thermally expandable graphite and the inorganic filler is 30% by weight or more, and the content of the thermally expandable graphite is 5% by weight or more. .

The present invention includes the following aspects.

Section 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,
The particle size ratio between the particle size of the thermally expandable graphite and the particle size of the inorganic filler is in the range of 1 to 1000, and the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more. and a heat-expandable graphite content of 15% by weight or more.

In item 2, a fire-resistant resin composition containing a matrix component that is a resin, elastomer, rubber, or a combination thereof, thermally expandable graphite, and an inorganic filler,
The particle size ratio between the particle size of the thermally expandable graphite and the particle size of the inorganic filler is in the range of 1 to 1000, and the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more. and a heat-expandable graphite content of 5% by weight or more.

Item 3. Item 3. The fire resistant resin composition according to Item 1 or 2, wherein the thermally expandable graphite has an average particle size of 100 μm or more.

Section 4. Item 4. The fire-resistant resin composition according to any one of Items 1 to 3, wherein the inorganic filler comprises a phosphite.

Item 5. Item 5. The fire resistant resin composition according to any one of Items 1 to 4, further comprising a polyphosphate.

Item 6. Item 6. The fire resistant 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. A fire-resistant resin molded article made of the fire-resistant resin composition according to any one of Items 1 to 7.

Item 9. A fitting comprising the fire-resistant resin molded article according to Item 8.

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

1 is a schematic front view showing a fire-resistant window in which a sash frame is provided with a fire-resistant resin molding made of the fire-resistant resin composition of the present invention; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

Matrix components may be any of resins, elastomers, and rubbers. Resins include thermoplastic resins and thermosetting resins.

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

Any of the above thermoplastic resins may be crosslinked or modified to the extent that the fire resistance of the resin composition is not impaired. The method of crosslinking the resin is also not particularly limited, and conventional crosslinking methods for thermoplastic resins, such as crosslinking using various crosslinking agents and peroxides, and crosslinking by electron beam irradiation, can be used.

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

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

These epoxy group-containing monomers may be used alone, or two or more of them may be used in combination.

As the curing agent, a polyaddition type or a catalyst type is used. Examples of polyaddition type curing agents include polyamines, acid anhydrides, polyphenols, and polymercaptans. Examples of the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes. A method for curing the epoxy resin is not particularly limited, and a known method can be used.

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

Rubber substances 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 ), chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, urethane rubber, and the like. Among them, butyl rubber is preferred.

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

Among these synthetic resins and/or rubber substances, polyvinyl chloride-based resins such as polyvinyl chloride resins and chlorinated polyvinyl chloride resins are preferable from the viewpoint of being able to contain a large amount of plasticizer and having excellent kneading efficiency. . Polyolefin-based resins such as ethylene-vinyl acetate copolymer resin (EVA) are also preferable from the viewpoint that the processing temperature can be lowered and the expanded graphite can be kneaded without applying a load.

Thermally expandable graphite is a conventionally known substance that has the property of expanding when heated. Powders such as natural flake graphite, pyrolytic graphite, Kish graphite, etc. are combined with inorganic acids such as concentrated sulfuric acid, nitric acid, selenic acid, concentrated nitric acid, perchloric acid, perchlorate, permanganate, bichromate, A graphite intercalation compound is produced by treating with a strong oxidizing agent such as bichromate and hydrogen peroxide, and is a type of crystalline compound that maintains the layered structure of carbon.

The thermally expandable graphite obtained by acid treatment as described above may be further neutralized with ammonia, lower aliphatic amines, alkali metal compounds, alkaline earth metal compounds and the like.

The larger the grain size (particle size) of the thermally expandable graphite, the greater the expansion performance and the more favorable the fire resistance. However, the larger the particle size, the more difficult it is to disperse in the matrix, and the longer it takes to knead. From the viewpoint of expansion ratio, the particle size of the thermally expandable graphite is preferably 100 μm or more, more preferably 400 μm or more. Although the upper limit of the gold particle size of the thermally expandable graphite is not particularly limited, it is preferably 1500 μm or less, 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 commercially available thermally expandable graphite classified through a predetermined sieve. The average particle size was defined as the particle size of 50% of the accumulated particles passing through from the small particle size side of the raw material used. Alternatively, a 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 passing amount from the small particle size side is integrated 50 % particle diameter can be determined as the average particle diameter.

The content of the thermally expandable graphite is not particularly limited, but it is preferably 10 to 500 parts by weight with respect to 100 parts by weight of the matrix component, 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, the coefficient of volume expansion is large, and the fireproof performance of filling the burned-out portions of structures such as sashes is exhibited.

When the expansion heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and acts like an aggregate to improve the strength of the expansion 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 and magnesium hydroxide. , aluminum hydroxide and hydrotalcite; and 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 sulfate, gypsum fiber, calcium salts such as calcium silicate; silica, diatomaceous earth, dawsonite, 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, dewatered 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. Hydrous inorganics include alkaline earth metal hydroxides.

As an inorganic filler, a compound having flame retardancy (flame retardant) such as a phosphorus compound may be added. The addition of a phosphorus compound increases the strength of the expansion insulation layer and improves the fireproof performance. The phosphorus compound is not particularly limited. metal phosphates such as sodium phosphate, potassium phosphate and magnesium phosphate; and compounds represented by the following chemical formula (1).

In chemical formula (1), R ¹ and R ³ each represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ² is a hydroxyl group with 1 to 16 carbon atoms
represents 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.

Commercially available red phosphorus can be used as the red phosphorus, but from the viewpoint of safety such as moisture resistance and no spontaneous ignition during kneading, red phosphorus particles whose surfaces are coated with a resin are preferably used.

The compound represented by the chemical formula (1) is not particularly limited, and examples thereof include 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 acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid and the like. Among them, t-butylphosphonic acid is expensive, but is preferred in terms of high flame retardancy. The above phosphorus compounds may be used alone or in combination of two or more.

Alternatively, salts of lower phosphoric acids such as primary phosphoric acid, secondary phosphoric acid, tertiary phosphoric acid, metaphosphoric acid, phosphorous acid and hypophosphorous acid may be used. As used herein, salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; other metal salts such as aluminum salts; Aluminum salts of phosphorous acid are preferred from the viewpoint of fire resistance.

The particle size of the inorganic filler is preferably 0.5-200 μm, more preferably 1-10 μm. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance. When the addition amount is large, the viscosity of the resin composition increases and the moldability decreases as the filling progresses. A large diameter is preferable, but a particle diameter of 100 μm or less is desirable from the viewpoint of the surface properties of the molded article and the mechanical properties of the resin composition. The average particle size was defined as the particle size of 50% of the accumulated particles passing through from the small particle size side of the raw material used. In addition, the cross-sectional SEM (scanning electron microscope image) of the prepared sheet was observed to obtain the particle size distribution of the inorganic filler, and in the volume-based particle size distribution obtained therefrom, the passing amount from the small particle size side was accumulated 50%. can also be used as the average particle size.

Further, in order to obtain a desired particle size, it is also possible to crush the aggregated inorganic filler, disperse it with a solvent or the like, and then add it or sieve it.

Examples of inorganic fillers include, for aluminum hydroxide, "Higilite H-31" (manufactured by Showa Denko) with a particle size of 18 µm, "B325" (manufactured by ALCOA) with a particle size of 25 µm, and calcium carbonate with a particle size of 1.8 μm “Whiten SB Red” (manufactured by Bihoku Funka Kogyo Co., Ltd.), 8 μm particle size “BF300” (manufactured by Bihoku Funka Kogyo Co., Ltd.), and the like.

Although the content of the inorganic filler is not particularly limited, it is preferably 30 to 500 parts by weight per 100 parts by weight of the matrix component. When the content is 30 parts by weight or more, sufficient fireproof performance is obtained, and when the content is 500 parts by weight or less, the mechanical strength is maintained. The content of the inorganic filler is more preferably 40-350 parts by weight.

When a 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 per 100 parts by weight of the matrix component. When the amount is 30 parts by weight or more, the effect of improving the strength of the expansion 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 40-250 parts by weight.

The fire-resistant resin composition of the present invention may further contain polyphosphate as an inorganic filler. Polyphosphates also function as flame retardants. Polyphosphates include 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 “Terage C60” manufactured by Chisso.

A preferable ammonium polyphosphate is surface-coated ammonium polyphosphate (also referred to as coated ammonium polyphosphate). A silane-coated ammonium polyphosphate surface-coated with silane is described in JP 2000-63562. Melamine-coated ammonium polyphosphate includes (a) melamine-coated ammonium polyphosphate in which melamine is added and/or attached to the surface of powdery ammonium polyphosphate particles, and (b) melamine molecules present in the coating layer of the melamine-coated ammonium polyphosphate particles. Coated ammonium polyphosphate in which the particle surface is crosslinked by active hydrogen possessed by an amino group therein and a compound having a functional group capable of reacting with the active hydrogen, and/or (c) powdery ammonium polyphosphate or the melamine It is a coated ammonium polyphosphate in which the surface of coated ammonium polyphosphate particles is coated with a thermosetting resin. Examples of commercially available melamine-coated ammonium polyphosphate particles include "AP462" manufactured by Clariant, "FR CROS 484" manufactured by Budenheim Iberica, "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 size of the coated ammonium polyphosphate is preferably 15-35 μm. The average particle size of the coated ammonium polyphosphate can be measured by laser diffraction particle size distribution measurement.

In the fire-resistant resin composition of the present invention, the particle size ratio between the particle size of the thermally expandable graphite and the particle size of the inorganic filler is 1-1000. Within this range, the thermally expandable graphite with a large particle size can be efficiently dispersed in the matrix resin without being disturbed by the inorganic filler, and the inorganic filler can be dispersed between the thermally expandable graphite dispersed in the resin. As a result of the dispersion of the filler and the good dispersion of the inorganic filler, kneading efficiency is improved. The particle size ratio is preferably 3-500, more preferably 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 this range, the dispersion of the thermally expandable graphite in the matrix is insufficient, causing problems such as surface contamination and unevenness.

Moreover, in the fire-resistant resin composition of the present invention, the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more, preferably 50% by weight or more. Although the upper limit of the total content of the thermally expandable graphite and the inorganic filler is not particularly limited, it is 75% by weight or less, preferably 60% by weight or less. By setting it as such a numerical range, the outstanding fire resistance can be expressed.

Further, in the fire-resistant resin composition of the present invention, the content of thermally expandable graphite is 5% by weight or more,
It is more preferably 15% by weight or more, still more preferably 20% by weight or more, and most preferably 25% by weight or more. Although the upper limit of the content of thermally expandable graphite is not particularly limited, it is 75% by weight or less and 50% by weight or less. By setting it as such a numerical range, the outstanding fire resistance can be expressed.
In a preferred embodiment of the present invention, when the matrix component is a synthetic resin and an elastomer, the content of thermally expandable graphite is 15% by weight or more, preferably 20% by weight or more, and more preferably 25% by weight or more. is.
In another preferred embodiment, when the matrix component is rubber, the content of thermally expandable graphite is 5% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more, and further Preferably, it is 25% by weight or more.

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

Plasticizers are added to adjust the melt viscosity of matrix components, particularly thermoplastic resins. A plasticizer can also be rephrased as a softening agent. As the plasticizer, one or a combination of two or more plasticizers exemplified below may be used:
Di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or higher or mixed alcohols having about 10 to 13 carbon atoms A phthalate plasticizer such as a phthalate of;
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 and di-2-ethylhexyl sebacate ester plasticizer;
trimellitates such as tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellitate acid ester plasticizer;
adipate plasticizers such as di-2-ethylhexyl adipate (DOA) and diisodecyl adipate (DIDA);
Sebacate plasticizers such as dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate (DOS);
tributyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate , tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate and other phosphate ester plasticizers;
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 resins;
chlorinated paraffins;
chlorinated fatty acid esters such as pentachlorinated stearic acid alkyl esters; and process oils such as paraffinic process oils, naphthenic process oils and aromatic process oils.

Although the content of the plasticizer in the fire-resistant resin composition is not particularly limited, it is preferably in the range of 25 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Further, the fire-resistant resin composition of the present invention may be added with heat stabilizers, lubricants, processing aids, thermally decomposable foaming agents, antioxidants, antistatic agents, pigments, etc., within a range that does not impair its physical properties. may

Examples of heat stabilizers include lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, and dibasic lead stearate; organic tin heat stabilizers such as tin malate, organic tin laurate and dibutyl tin malate; metal soap heat stabilizers such as zinc stearate and calcium stearate; You may use together.

Examples of lubricants 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 two or more of them may be used in combination.

Processing aids include, for example, chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, high molecular weight polymethyl methacrylate, and the like.

Thermal decomposition type blowing agents include, for example, azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), p,p-oxybisbenzenesulfonylhydrazide (OBSH), azobisisobutyronitrile (AIBN), and the like. mentioned.

The fire-resistant resin composition of the present invention can be melt extruded with an extruder such as a single-screw extruder or a twin-screw extruder to obtain a fire-resistant resin molded article. The melting temperature varies depending on the matrix component and is not particularly limited, but for example, it is 130 to 170°C in the case of polyvinyl chloride resin.

The fire-resistant resin composition or fire-resistant resin molded article of the present invention imparts fire resistance to fittings such as windows, shoji screens, doors (that is, doors), doors, sliding doors, and transoms; ships; and structures such as elevators. can be used for Since the refractory resin composition of the present invention has excellent moldability, it is possible to easily obtain a deformed molded article adapted to a complicated shape of a structure. FIG. 1 shows an example in which the fire-resistant resin molding 4 of the present invention is applied to a sash frame of a window 1 as fittings. In this example, the sash frame has two inner frames 2 and one outer frame 3 surrounding the inner frame 2, and along each side of the frame body of the inner frame 2 and the outer frame 3, the inner frame 2 and a fire-resistant resin molding 3 is attached inside the outer frame 3 . In this manner, by providing the fire-resistant resin molding 3 of the present invention, the window 1 can be provided with fire resistance.

The present invention is not limited to the above-described embodiments, and for example, the following embodiments can be adopted.
When rubber (for example, butyl rubber) is used as the matrix resin, the content of thermally expandable graphite is preferably 5% by weight or more and 10% by weight or less. The total content of the thermally expandable graphite and the inorganic filler is preferably 30% by weight or more and 70% by weight or less.

Further, the particle size ratio between the particle size of the thermally expandable graphite and the particle size of the inorganic filler may be in the range of 1 to 1000, preferably 30 to 700, more preferably 50 to 200, It is more preferably 65-75.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these.

1. Preparation of fireproof sheet [Example 1]
With 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, granular After mixing 100 parts by weight of aluminum phosphite (diameter: 800 μm) and 50 parts by weight of aluminum phosphite (particle diameter: 100 μm) as an inorganic filler in a kneader, the mixture was formed into a sheet with a calender roll to form a sheet having a width of 1000 mm. A fire-resistant sheet was obtained as a fire-resistant resin molding having a thickness of 1.5 mm and a length of 1 m. Also, the kneading time in the kneader was standardized to 5 minutes after the graphite was added, and the tests were carried out.

[Examples 2 to 33 and Comparative Examples 1 to 4]
For Examples 2 to 33 and Comparative Examples 1 to 4, the components were mixed in the amounts shown in Tables 1 to 3 and formed into sheets in the same manner as in Example 1 to obtain fireproof sheets.

2. Measurement of fire resistance (expansion ratio) From the obtained refractory sheet, samples were taken from three points, the central part / central part in front of the flow method, and the central part in the back of the flow direction, and a test piece (length 100 mm, width 100 mm, thickness 1.5 mm) in a predetermined holder, supplied to an electric furnace, heated at 600 ° C. for 30 minutes, then measured the thickness of the test piece, (thickness of test piece after heating) / (before heating (thickness of the test piece) was calculated as the expansion ratio. When the difference between the minimum value and the maximum value was within 5% of the average, it was rated as ⊚, when it was within 10%, and when it was 10% or more, x.

3. Evaluation of Surface Finish of Fire Resistant Sheet The surface finish of the fire resistant sheets of Examples 1 to 10 and Comparative Examples 1 and 2 was evaluated by visually confirming surface roughness and dirt. Surface roughness (presence or absence of cracks and cracks) and contamination (surface exposure of powder) were evaluated by visual confirmation. Wrinkles and cracks were defined as having a size of 3 mm or more, and powder exposure was defined as a white surface on a black sheet surface, or a graphite exposed area of 4 mm ² or more. A sheet with a width of 100 cm × 100 cm was evaluated as ○ if it was 5 or less, and as × if it was 3 or more:
◯: No wrinkles on the surface or 5 or less wrinkles of 3 mm or more per m ² ×: 5 or more wrinkles of 3 mm or more per m ² on the surface.

4. Evaluation of strength The breaking strength of the obtained fireproof sheet was measured according to JIS K 7161, and the tensile strength in the machine direction of the roll was measured. When the strain reached 110%, the sample was broken.

The refractory sheets of Examples 1 to 33 were excellent in surface finish, and their deterioration in quality was suppressed.

Claims (9)

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,
The particle size ratio between the particle size of the thermally expandable graphite and the particle size of the inorganic filler is in the range of 1 to 1000, and the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more. and a heat-expandable graphite content of 15% by weight or more. 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,
The particle size ratio between the particle size of the thermally expandable graphite and the particle size of the inorganic filler is in the range of 1 to 1000, and the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more. and a heat-expandable graphite content of 5% by weight or more. 3. The fire-resistant resin composition according to claim 1, wherein the thermally expandable graphite has an average particle size of 100 [mu]m or more. 4. The fire-resistant resin composition according to any one of claims 1 to 3, wherein the inorganic filler comprises a phosphite. 5. The fire resistant resin composition according to any one of claims 1 to 4, further comprising a polyphosphate. 6. The fire resistant resin composition according to any one of claims 1 to 5, further comprising a plasticizer. 7. The fire-resistant resin composition according to any one of claims 1 to 6, wherein the matrix component is a polyvinyl chloride resin or a polyolefin resin. A fire-resistant resin molded article made of the fire-resistant resin composition according to any one of claims 1 to 7. A fitting comprising the fire-resistant resin molding according to claim 8 .