JP2017133007A - Fire-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fire-resistant resin composition which has less variation in fire resistance, and is excellent in surface finishing and strength.SOLUTION: There is provided a fire-resistant resin composition which contains a matrix component being a resin, an elastomer, a rubber or a combination thereof, thermally expandable graphite and an inorganic filler, where the fire-resistant resin composition contains 0.02-1 pts.mass of at least one selected from the group consisting of polymethyl methacrylate, modified polymethyl methacrylate and chlorinated polyethylene with respect to 1 pts.mass of the thermally expandable graphite.SELECTED DRAWING: 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, if the refractory material containing thermally expanded graphite does not shorten the processing time, the components in the thermally expanded graphite are lost and the expansion ratio is lowered, so that it is necessary to shorten the processing time. On the other hand, refractory materials often contain a large amount of inorganic fillers and flame retardant materials in combination with thermally expanded graphite, and in order to mix these into the binder resin, it is necessary to knead firmly, and kneading is insufficient. This causes problems that the refractory material becomes brittle, the surface becomes dirty (powder is blown / black), and handling is hindered. Further, there may be variations in fire resistance depending on the sampling position of the fireproof material.

  Even if the kneading is insufficient, it has been proposed to solve the problem by stacking such as sandwiching with a non-woven fabric, but it is not always satisfactory due to cost increase and generation of wrinkles.

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 little variation in fire resistance, excellent surface finish, and excellent strength.

  In order to achieve the above-mentioned object, the present inventor has added at least one substance selected from chlorinated polyolefin and acrylic polymer in the refractory resin composition in an amount of 0. It has been found that the above-mentioned problems can be solved by including the compound at a ratio of 02 to 1 part by mass, and the present invention has been completed.

  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,
Fire resistance characterized by containing at least one selected from the group consisting of polymethyl methacrylate, modified polymethyl methacrylate and chlorinated polyethylene in a ratio of 0.02 to 1 part by mass with respect to 1 part by mass of thermally expandable graphite. Resin composition.

  Item 2. Item 2. The fireproof resin composition according to item 1, wherein the substance is at least one selected from the group consisting of chlorinated polyethylene, methacrylate ester copolymer, and methacrylate ester copolymer modified product. .

  Item 3. Item 3. The fire resistant resin composition according to Item 1 or 2, wherein the substance has a weight average molecular weight of 100,000 or more.

  Item 4. Item 4. The fireproof resin composition according to any one of Items 1 to 3, wherein the inorganic filler includes a phosphite.

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

  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 fireproof resin composition according to any one of Items 1 to 6, wherein the matrix component is a vinyl chloride 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.

  According to the present invention, there is provided a fire resistant resin composition having little variation in fire resistance, excellent surface finish, and excellent strength.

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. Polymer resin, ethylene-vinyl acetate copolymer resin (EVA), polyolefin resin such as 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, novolac resin, polyurethane resin, polyisobutylene and the like.

  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, 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, chlorosulfonated polyethylene, acrylic rubber And rubber materials such as epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicon rubber, fluororubber, and urethane rubber. Of these, butyl rubber is preferred.

  These resins, elastomers, and / or rubber substances can be used alone or in combination of two or more.

  Among these resins, elastomers, and / or rubber substances, polyvinyl chloride resins and polyolefin resins (for example, ethylene-vinyl acetate copolymer) are preferable from the viewpoint of dispersibility of expanded graphite in a matrix resin.

  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 particle size can be controlled by using commercially available thermally expandable graphite classified by a predetermined sieve.

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

  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.

  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.

  In order to obtain a desired particle size, the aggregated inorganic filler can be finely divided, dispersed with a solvent or the like, and then controlled by charging, sieving, or the like.

  As the inorganic filler, for example, for aluminum hydroxide, “Hijilite H-31” (manufactured by Showa Denko) having a particle size of 18 μm, “B325” (manufactured by ALCOA) having a particle size of 25 μm, and calcium carbonate, Examples include 1.8 μm “Whiteon SB Red” (manufactured by Bihoku Powdered Industries Co., Ltd.), “BF300” (manufactured by Bihoku Powdered Industries Co., Ltd.) having a particle size of 8 μm, and the like.

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

  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 mass with respect to 100 parts by mass of the matrix component. When the blending amount is 30 parts by mass or more, the effect of improving the strength of the expanded heat insulating layer is sufficient, and when it is 300 parts by mass or less, the mechanical strength is maintained. The content of the phosphorus compound is more preferably 40 to 250 parts by mass.

  Among inorganic fillers, specific examples of aluminum hydroxide include, for example, aluminum hydroxide, “Hijilite H-31” (manufactured by Showa Denko) having a particle size of 18 μm, and “B325” (ALCOA) having a particle size of 25 μm. In the case of calcium carbonate, “Whiteon SB Red” (manufactured by Bihoku Flour Industry Co., Ltd.) having a particle size of 1.8 μm, “BF300” (manufactured by Bihoku Flour Industries Co., Ltd.) having a particle size of 8 μm and the like can be mentioned.

  In one preferred embodiment of the refractory 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. 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 range, the expanded graphite is not sufficiently dispersed in the matrix, which causes problems such as surface contamination.

  Moreover, in one of the preferable aspects of the fireproof resin composition of this invention, content of the sum total of thermally expansible graphite and an inorganic filler is 30 mass% or more. Preferably it is 50 mass% or more. By setting it as such a numerical value range, the outstanding fire resistance can be expressed.

  Moreover, in one of the preferable aspects of the fireproof resin composition of this invention, content of a thermally expansible graphite is 15 mass% or more, Preferably it is 20 mass% or more, More preferably, it is 25 mass% or more. By setting it as such a numerical value range, the outstanding fire resistance can be expressed.

  The refractory resin composition of the present invention contains one or more substances selected from chlorinated polyolefins and acrylic polymers (hereinafter sometimes referred to as “component (A)”).

  By containing the component A, it is considered that the component (A) interacts with both the matrix resin and the thermally expandable graphite, and the thermally expandable graphite can be efficiently dispersed in the matrix resin in a short time. .

  Examples of the chlorinated polyolefin include chlorinated polyethylene, chlorinated polypropylene, and chlorinated EVA. When the matrix resin is a polyvinyl chloride resin, dispersibility by chlorinated polyolefin is particularly preferable.

  Acrylic polymers include acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate, and ethyl methacrylate, n-butyl methacrylate, It is a group of polymers composed of a copolymer mainly composed of at least one of methacrylic acid esters such as methacrylic acid-2-ethylhexyl.

  Among acrylic polymers, methacrylic acid ester copolymers are desirable from the viewpoint of dispersion effect.

The methacrylate ester copolymer has a general formula:
_{(CH 2 C (CH 3)} COOCH 3) n - (CH 2 CHCOOR)
(Wherein R is an alkyl group)
And
{CH ₂ C (CH ₃ ) COOCH ₃ )-(CH ₂ CHCOOR)} _n
(Wherein R is an alkyl group)
Is mentioned.

  Examples of the former include α-methylstyrene-acrylonitrile copolymer (Mitsubrene H-605, Mitsubishi Rayon Co., Ltd.), methyl methacrylate-maleimide copolymer (Metbrene H-630, Mitsubishi Rayon Co., Ltd.), and the latter (alkyl acrylate copolymer). Examples of coalescence include Mitsubishi Rayon's Metabrene P530, Metabrene P551, and the like.

  Examples of the modified polymethyl methacrylate include acid-modified polymethyl methacrylate with maleic anhydride. And methacrylate polytetrafluoroethylene resin (Mitsubishi Rayon A-3000).

  In the present invention, as the component (A), it is preferable to use one or more selected from the group consisting of chlorinated polyethylene, methacrylic ester copolymer, and modified methacrylic ester copolymer.

  The molecular weight of the component (A) is not particularly limited, but the mass average molecular weight is preferably 100,000 or more, more preferably 1,000,000 or more.

    The ratio of the mass of the component (A) and the thermally expandable graphite is 0.02 to 1 part by mass of the component (A) with respect to 1 part by mass of the thermally expandable graphite. The lower limit is preferably 0.03 parts by mass. Moreover, it is preferable that an upper limit is 0.5 mass part.

  In addition, two or more components (A) can be used in combination, and in that case, the dispersion effect can be further improved.

    Although not restricting the present invention, the refractory resin composition of the present invention has a component (A) that functions as a dispersant for the heat-expandable graphite. Is not sufficient, and it is considered that a good surface finish can be achieved.

    As an embodiment of the component (A), polymethyl methacrylate (PMMA) having a weight average molecular weight of 1,000,000 or more can be used. Use of PMMA having a weight average molecular weight of 1,000,000 or more is preferable because the pseudo-crosslinking point is increased and the strength of the molded product obtained from the refractory resin composition is improved.

    As one embodiment of polymethyl methacrylate, PMMA having a weight average molecular weight of less than 1,000,000 can be used. The use of PMMA having a weight average molecular weight of less than 1,000,000 is preferable because the gelation speed of the refractory resin composition is improved.

    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, 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. Examples of commercially available melamine-coated ammonium polyphosphate particles include “AP462” manufactured by Clariant, “FR CROS 484” and “FR CROS 487” manufactured by Budenheim Iberica. 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.

    Although content of the plasticizer in a refractory resin composition is not specifically limited, It is preferable to exist in the range of 25-100 mass parts with respect to 100 mass parts of said thermoplastic resins.

    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. Also good.

    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 refractory resin composition of the present invention can be obtained by a melt extrusion with 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 used to impart fire resistance to structures such as windows, shojis, doors (that is, doors), doors, brans, and bams; ships; and structures such as elevators. Can be used. Since the refractory resin composition of the present invention has excellent moldability, it is possible to easily obtain a modified molded body adapted to the complex 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 compounding amounts shown in Table 1, 100 parts by mass of polyvinyl chloride as synthetic resin (matrix component), 6 parts by mass of polymethyl methacrylate (PMMA), 80 parts by mass of diisodecyl phthalate (DIDP) as plasticizer, 100 of thermally expandable graphite After mixing mass part, 50 parts by mass of ammonium polyphosphate, and 50 parts by mass of calcium carbonate as an inorganic filler with a kneader, the mixture was formed into a sheet with a calender roll, width 150 mm, thickness 1.5 mm, long A fire resistant sheet as a fire resistant resin molding having a thickness of 5 m was obtained. The kneader kneading time was set to 5 minutes after the graphite was added, and the test was conducted.
[Examples 2-36, Comparative Examples 1-2]
For Examples 2-36 and Comparative Examples 1-2, the components were mixed and extruded at the blending amounts shown in Table 1 to obtain fireproof sheets.

2. Measurement of fire resistance (expansion magnification) From the obtained fireproof sheet, the first part in the length direction (0 to 1 m with one end as 0 m), the center part (2.5 m in the length direction), the part of 4 to 5 m , Sample pieces (length 100 mm, width 100 mm, thickness 1.5 mm) were put in a predetermined holder, supplied to an electric furnace, heated at 600 ° C. for 30 minutes, and then the thickness of each test piece Was measured, and (thickness of the test piece after heating) / (thickness of the test piece before heating) was calculated as an expansion ratio. The difference between the minimum value and the maximum value of the samples prepared from the three locations varies within 5% of the average value of the expansion ratios at the three locations. It was.

3. Evaluation of surface finish of fireproof sheet The surface finish of the obtained fireproof sheet was evaluated by visual confirmation of surface roughness (presence of wrinkles). The definition of wrinkles was defined as a size of 3 mm or more. In the prepared sheet having a width of 15 cm × 500 cm, it was rated as ○ if the wrinkle was within 4 places, and x if it was 5 or more.

○: No wrinkle on the surface of the prepared sheet or 4 or less wrinkles of 3 mm or more ×: 5 or more wrinkles of 3 mm or more on the surface of the prepared sheet Evaluation of strength The breaking strength of the obtained fireproof sheet was measured according to JIS K 7161, and the tensile strength in the flow direction of the roll was measured. A case where the strain was not 110% and a case where the strain was broken were taken as x.

Claims (9)

  At least one substance selected from chlorinated polyolefins and acrylic polymers 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 In a ratio of 0.02 to 1 part by mass with respect to 1 part by mass of thermally expandable graphite.   2. The refractory resin composition according to claim 1, wherein the substance is at least one selected from the group consisting of chlorinated polyethylene, methacrylate ester copolymer, and modified methacrylate copolymer. object.   The refractory resin composition according to claim 1 or 2, wherein the substance has a weight average molecular weight of 100,000 or more.   The refractory resin composition according to any one of claims 1 to 3, wherein the inorganic filler includes phosphite.   The refractory resin composition according to claim 1, further comprising a polyphosphate.   The fireproof resin composition according to any one of claims 1 to 5, further comprising a plasticizer.   The fireproof resin composition according to any one of claims 1 to 6, wherein the matrix component is a vinyl chloride resin.   A fireproof resin molded article comprising the fireproof resin composition according to any one of claims 1 to 7.   A joinery comprising the fireproof resin molded article according to claim 8.

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