JP7323280B2 - Fire-resistant resin composition and fire-resistant resin molding - Google Patents

Description

The present invention relates to a fire-resistant resin composition and a fire-resistant resin molding.

2. Description of the Related Art In the field of construction, a fireproof resin composition obtained by mixing an inorganic material that expands when heated into a matrix resin is used for construction materials such as fittings, columns, and wall materials for fire prevention. Such a refractory resin composition and a refractory resin molded article formed therefrom expand when heated, and the combustion residue forms a refractory and heat insulating layer, thereby exhibiting refractory and heat insulating performance.

Patent Document 1 describes a base rubber component composed of 30 to 60 parts by mass of liquid rubber and 40 to 70 parts by mass of butyl rubber, and 3 to 50 parts by mass of a tackifier per 100 parts by mass of the base rubber component.
10 to 100 parts by mass of thermally expandable graphite, 30 to 180 parts by mass of flame retardant, 30 to 30 parts by mass of inorganic filler
210 parts by mass, 0.1 to 10 parts by mass of a vulcanizing agent, and 0.1 to 10 parts by mass of a vulcanization accelerator. is disclosed. The fire-resistant rubber composition may contain 1-50 parts by weight of aluminum phosphite to improve shape retention.

JP 2009-138184

By the way, when the fire-resistant resin composition is used in a part exposed to rain or in a part with high humidity due to dew condensation, etc., the components in the fire-resistant resin composition may be eluted, resulting in deterioration of performance and poor appearance.

Patent Document 1 does not address water resistance.

An object of the present invention is to provide a fire-resistant resin composition excellent in fire resistance and water resistance, and a fire-resistant resin molded article comprising the fire-resistant resin composition.

In order to solve the above problems, the following aspects of the present invention are provided.

Section 1. one or more matrix components selected from the group consisting of vinyl chloride resins and chlorinated vinyl chloride resins;
thermally expandable graphite;
one or more metal materials selected from the group consisting of metallic zinc, zinc oxide, zinc chloride, iron chloride, ferrocene, iron oxide and copper oxide;
containing an inorganic filler,
A fire-resistant resin characterized by containing 10 to 200 parts by weight of the thermally expandable graphite and 10 to 200 parts by weight of the total amount of the metal material and the inorganic filler with respect to 100 parts by weight of the matrix component. Composition.

Section 2. Item 2. The fire-resistant resin composition according to item 1, wherein the content of the water-soluble phosphorus compound in the fire-resistant resin composition is 10% by weight or less.

Item 3. Item 2. The fire-resistant resin composition according to Item 1, which contains substantially no water-soluble phosphorus compound.

Section 4. Item 4. The fire-resistant resin composition according to any one of items 1 to 3, wherein the content of the metal material in the fire-resistant resin composition is 0.1% by weight to 25% by weight.

Item 5. Item 5. The fire-resistant resin composition according to any one of Items 1 to 4, which contains a plasticizer, and the plasticizer is a plurality of plasticizers having different compatibility with the matrix component.
Item 6. Item 6. The fire-resistant resin composition according to any one of items 1 to 5, wherein the thermally expandable graphite has an average aspect ratio of 20 or more.
Item 7. Item 7. A fire-resistant resin molded article made of the fire-resistant resin composition according to any one of Items 1 to 6.

Item 8. A thermally expandable fire resistant sheet comprising the fire resistant resin composition according to any one of items 1 to 6.

Item 9. A fitting provided with the fire-resistant resin molding according to claim 7 or the thermally expandable fire-resistant sheet according to claim 8.

According to the fire-resistant resin composition of the present invention and the fire-resistant resin molded article made of the fire-resistant resin composition, it is possible to impart excellent fire resistance and water resistance to building fixtures and the like.

Schematic drawing which shows the example which constructed the heat-expandable fireproof sheet to the door.

The fire-resistant resin composition of the present invention comprises: one or more matrix components selected from the group consisting of polyvinyl chloride resins and polyvinyl chloride resins; thermally expandable graphite; metallic zinc, zinc oxide, zinc chloride, chloride 10 to 200 parts by weight of thermally expandable graphite per 100 parts by weight of the matrix component, containing one or more metal materials selected from the group consisting of iron, ferrocene, iron oxide and copper oxide; and 10 to 200 parts by weight of the total amount of the metal material and the inorganic filler.

Polyvinyl chloride resin (PVC) and polyvinyl chloride resin (CPVC) are fire resistant and serve as a matrix for mixing the other components of the fire resistant resin composition. The polyvinyl chloride resin may be obtained by polymerizing a vinyl chloride-based monomer that has been chlorinated before polymerization, or may be obtained by polymerizing a polyvinyl chloride resin and then chlorinating it. The method for chlorinating the polyvinyl chloride resin is not particularly limited, and conventionally known chlorinating methods can be used. For example, a thermal chlorination method, a photochlorination method, and the like can be mentioned. The degree of polymerization of polyvinyl chloride resins and polyvinyl chloride resins is preferably about 400 to 2500, more preferably about 400 to 2500, because if the degree of polymerization becomes small, the mechanical properties tend to deteriorate, and if it becomes large, the moldability tends to deteriorate. It is about 600-2000.

Thermally expandable graphite is a conventionally known substance that expands when heated. Powders such as natural flake graphite, pyrolytic graphite, and Kish graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, and concentrated nitric acid, perchloric acid, Graphite intercalation compounds are produced by treating with strong oxidizing agents such as perchlorates, permanganates, bichromates, and hydrogen peroxide, which are crystalline compounds that maintain the layered structure of carbon. be.

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

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.

Although the average aspect ratio of the thermally expandable graphite is not limited, it is preferably 20 or more.
When the average aspect ratio of the thermally expandable graphite is 20 or more, the water resistance of the fire-resistant resin composition can be further improved.
The average aspect ratio of the thermally expandable graphite is preferably 20 or more, more preferably 25 or more.
000 or less is preferable.

The average aspect ratio is the ratio of the average diameter in the horizontal direction to the thickness in the vertical direction.
Since thermally expandable graphite is generally flat, it can be seen that the vertical direction corresponds to the thickness direction and the horizontal direction corresponds to the radial direction. ratio.
Then, the aspect ratio is measured for a sufficiently large number, that is, 10 or more graphite pieces, and the average value is taken as the average aspect ratio. The average particle size of the thermally expandable graphite can also be obtained as the average value of the maximum horizontal dimension.
The maximum horizontal dimension of thermally expandable graphite and the thickness of exfoliated graphite can be measured using, for example, a field emission scanning electron microscope (FE-SEM).

The content of thermally expandable graphite in the fire-resistant resin composition is 10 to 200 parts by weight with respect to 100 parts by weight of the matrix component. If the content of the thermally expandable graphite is less than 10 parts by weight, expansion suitable for preventing the passage of fire may not be obtained, and if it exceeds 200 parts by weight, shape retention may deteriorate. be.

The particle size of the thermally expandable graphite is preferably 20-200 mesh. When the particle size is 200 mesh or less, the degree of expansion of the graphite is sufficient to obtain an expanded heat insulating layer. Good.

One or more metal materials selected from the group consisting of metallic zinc, zinc oxide, zinc chloride, iron chloride, ferrocene, iron oxide and copper oxide are added to improve flame retardancy of the fire resistant resin composition. In addition, these metal materials are less likely to cause a decrease in performance against exposure to moisture such as water and humidity compared to flame retardants containing phosphorus, and are preferable in terms of improving the water resistance of the fire-resistant resin composition. Zinc metal is Zn, zinc oxide is ZnO, zinc chloride is ZnCl ₂ , and iron chlorides include iron chloride (III) (FeCl ₃ ) and iron chloride (II) (FeCl ₂ ). Ferrocene is a compound represented _by Fe( _C5H5 ) ₂ . Iron oxides include iron (II) oxide and iron (III) oxide. Copper oxides include copper (I) oxide and copper (II) oxide.

The content of the metal material in the fire-resistant resin composition is preferably 5 to 195 parts by weight with respect to 100 parts by weight of the matrix component. 5 parts by weight or more is preferable from the viewpoint of shape retention effect of combustion residue, and 195 parts by weight or less is preferable from the viewpoint of moldability effect.

Also, the content of the metal material in the fire-resistant resin composition is preferably 0.1% by weight to 25% by weight. It is preferably 0.1% by weight or more from the viewpoint of shape retention of the combustion residue, and preferably 25% by weight or less from the viewpoint of moldability.

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,
For example, alumina, titanium oxide, calcium oxide, magnesium oxide, tin oxide, antimony oxide, metal oxides such as ferrite; metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite; metal carbonates such as magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate; inorganic phosphates as flame retardants; 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 balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders , potassium titanate, magnesium sulfate, lead zirconate titanate, zinc stearate, calcium stearate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dewatered sludge, etc. is mentioned. One or more of these inorganic fillers can be used. Metallic zinc, zinc oxide, zinc chloride and iron chloride are not included in inorganic fillers.

The particle size of the inorganic filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm.
μm. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance. It is preferably 5 μm or more. When the addition amount is large, the viscosity of the fire-resistant resin composition increases and the moldability decreases as the filling progresses, but the viscosity of the fire-resistant resin composition can be decreased by increasing the particle size. , Although a large particle size is preferred,
If the particle size exceeds 100 μm, the surface properties of the molded article and the mechanical properties of the resin composition deteriorate, so the particle size is preferably 100 μm or less.

The content of the inorganic filler in the fire-resistant resin composition is preferably 5 to 195 parts by weight with respect to 100 parts by weight of the matrix component. The content of the inorganic filler is preferably 5 parts by weight or more with respect to 100 parts by weight of the matrix component from the viewpoint of the effect of imparting flame retardancy (reduction of the amount of combustible components), and from the viewpoint of maintaining mechanical properties, 100 parts by weight of the matrix component. It is preferably not more than 195 parts by weight.

The fire-resistant resin composition of the present invention contains 10 to 200 parts by weight of the total amount of the metal material and the inorganic filler with respect to 100 parts by weight of the matrix component. If it is less than 10 parts by weight, the fire resistance may be poor, and if it exceeds 200 parts by weight, moldability may be impaired. Also, the ratio of the metal material to the inorganic filler is preferably from 50:1 to 1:50.

The total content of the metal material and the inorganic filler (thermally expandable graphite: (metal material + inorganic filler)) with respect to the content of thermally expandable graphite is 1:0.5 to 10 by weight. is preferred. If the weight ratio is less than 1:05, sufficient fire resistance may not be obtained. If the weight ratio is more than 1:10, the mechanical properties may deteriorate and the strength may be insufficient.

The fire-resistant resin composition of the present invention can contain resins, elastomers and rubbers other than the above matrix components. Resins other than the matrix component include thermoplastic resins, thermosetting resins, and combinations thereof.

Examples of thermoplastic resins include polypropylene resin, polyethylene resin, poly(1-
) polyolefin resins such as butene resins and polypentene resins, polyester resins such as polyethylene terephthalate, polystyrene resins, acrylonitrile-butadiene-styrene (
ABS) resin, ethylene vinyl acetate copolymer (EVA), polycarbonate resin, polyphenylene ether resin, (meth)acrylic resin, polyamide resin, novolak resin, polyurethane resin, polyisobutylene and other synthetic resins.

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.

Examples of elastomers include olefin-based elastomers, styrene-based elastomers, ester-based elastomers, amide-based elastomers, vinyl chloride-based elastomers, and combinations thereof.
Rubbers 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.

Each of these resins, elastomers and rubbers can be used alone or in combination of two or more. Combinations of resins, elastomers, and rubbers can also be used.

The fire-resistant resin composition of the present invention can further contain a phosphorus compound in order to increase the strength of the expandable heat-insulating layer and improve the fireproof performance. The phosphorus compound is not particularly limited, and examples thereof include red phosphorus; various phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate; aluminum phosphite; Phosphite metal salts such as; sodium phosphate,
Phosphate metal salts such as potassium phosphate and magnesium phosphate; ammonium polyphosphate; compounds represented by the following chemical formula (1); Among these, red phosphorus, ammonium polyphosphate, and the compound represented by the following chemical formula (1) are preferable from the viewpoint of fire resistance.

In chemical formula (1), R ¹ and R ³ are the same or different and 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, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon It represents an aryloxy group of numbers 6-16.
The compound represented by the chemical formula (1) is not particularly limited, and examples thereof include methylphosphonic acid,
dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, n-propylphosphonic acid, n-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, phenylphosphinic 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 two or more of them may be used in combination.
Although the content of the phosphorus compound is not limited, it is 0 to 5 parts per 100 parts by weight of the matrix resin.
It is preferably 0 parts by weight.

The fire-resistant resin composition of the present invention may further contain a plasticizer (except for the above phosphorus compound).
The plasticizer is not particularly limited, and for example, one or a combination of two or more plasticizers exemplified below can 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;
Di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA)
, dibutyl adipate (DBA), di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, etc. agent;
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;
Di-2-ethylhexyl adipate (DOA) and diisodecyl adipate (DIDA
) and other adipate plasticizers;
Sebacate plasticizers such as dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate (DOS);
trimethyl phosphate, triethyl phosphate, 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, tris(2-ethylhexyl) phosphate, tri Phosphate ester plasticizers such as phenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl 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 resins;
chlorinated paraffins; and chlorinated fatty acid esters such as pentachlorinated stearic acid alkyl esters.

Among the above plasticizers, phthalic acid-based plasticizers are preferred from the viewpoint of flame retardancy and economy.

When two or more of the above plasticizers are used in combination, it is preferable to include a plurality of plasticizers having different compatibility with the matrix component.
When two or more plasticizers are used in combination, the difference in the compatibility parameter (SP value) calculated by the small method between the matrix component and the plasticizer is greater than 0.5, and the matrix component and the plasticizer and a plasticizer having a compatibility parameter difference of 0.5 or less calculated by the small method.
A plurality of plasticizers with different compatibility are used together, and further sm
A plasticizer having a compatibility parameter difference of more than 0.5 calculated by the all method and a plasticizer having a compatibility parameter difference of 0.5 or less calculated by the small method between the matrix component and the plasticizer. By using them together, a fire-resistant resin composition having more excellent water resistance can be obtained.

When the amount of the plasticizer added is small, the extrusion moldability tends to be lowered, and when the amount is large, the molded article obtained tends to be too soft. For this reason, the content of the plasticizer is not limited,
It is preferably 0 to 200 parts by weight with respect to 100 parts by weight of the matrix resin. In one embodiment, when the matrix resin is a polyvinyl chloride resin or a polyvinyl chloride resin, the content of the plasticizer may be 20-200 parts by weight with respect to 100 parts by weight of the matrix resin. In another embodiment, when the matrix resin is a polyvinyl chloride resin or a polyvinyl chloride resin, the content of the plasticizer can be 20-100 parts by weight with respect to 100 parts by weight of the matrix resin.

Examples of the other components that can be contained in the fire-resistant resin composition include bromine-based, chlorine-based, nitrogen-based inorganic or organic flame retardants, phenol-based and amine-based flame retardants, as long as they do not impair the physical properties of the composition. , sulfur-based antioxidants, metal damage inhibitors, antistatic agents, stabilizers, cross-linking agents, lubricants, softeners, pigments, and the like.

The fire-resistant resin composition of the present invention preferably has a water-soluble phosphorus compound content as low as possible in order to suppress deterioration in performance against exposure to moisture such as water and humidity. The water-soluble phosphorus compound here means the weight loss rate due to elution when a mixture of 30% by weight of PVC, 20% by weight of DIDP, 25% by weight of expanded graphite, and 25% by weight of a phosphorus compound is immersed in pure water at 60°C for one week. is 3% or more. Specific examples of water-soluble phosphorus compounds include ammonium polyphosphate, ammonium phosphate, potassium phosphate, trisodium phosphate, ammonium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate, and dihydrogen phosphate. Examples include phosphorus compounds such as sodium, potassium dihydrogen phosphate, phosphoric acid, and phosphorous acid. In one embodiment, the content of the water-soluble phosphorus compound is 10% by weight or less in the fire-resistant resin composition. In another embodiment, the content of the water-soluble phosphorus compound is 1% by weight or less in the fire-resistant resin composition. In a further embodiment, the fire resistant resin composition is substantially free of water-soluble phosphorus compounds. Note that "substantially free of water-soluble phosphorus compounds" means that water-soluble phosphorus compounds are contained in an amount that may reduce the performance of the fire-resistant resin composition against exposure to moisture such as water and humidity. means to

Applying the fire-resistant resin composition obtained by mixing the above matrix component, thermally expandable graphite, metal material, inorganic filler, and other optional components to an object to be coated such as building fittings and drying the composition. A thermally expandable fireproof sheet having a desired thickness can be obtained. Coating is well known in the art. The thickness of the thermally expandable fireproof sheet is not particularly limited, but it is 0.2 to 10 mm.
is preferred. When the thickness is 0.2 mm or more, heat insulating properties are exhibited, and when the thickness is 10 mm or less, the handleability is good in terms of weight.

In addition, a fire-resistant resin molded article can be produced by molding a fire-resistant resin composition obtained by mixing the matrix component, thermally expandable graphite, metal material, inorganic filler, and other optional components. Molding includes press molding, extrusion molding and injection molding. Fireproof resin moldings include tight materials, glazing channels, packing such as gaskets, thermally expandable fireproof sheets, and the like. The thickness of the thermally expandable fireproof sheet is not particularly limited, but it is 0.2 to 10
mm is preferred.
Fire-resistant resin compositions, thermally expandable fire-resistant sheets, and fire-resistant resin moldings are particularly limited as long as they are thermally insulated by the expansion layer when exposed to high temperatures such as in the event of a fire, and the expansion layer has strength. not. It is preferable if the expansion ratio after heating for 30 minutes under the heating condition of 50 kW/m ² is 3 to 50 times. When the expansion ratio is 3 times or more, the burnt-out portion of the matrix component can be sufficiently buried, and when the expansion ratio is 50 times or less, the strength of the expansion layer is maintained and the effect of preventing flame penetration is obtained. be kept. The expansion ratio is calculated as (thickness of test piece after heating)/(thickness of test piece before heating) of the test piece of the fire-resistant resin composition, thermally expandable fire-resistant sheet, or fire-resistant resin molding. .
The thermally expandable fireproof sheet may be further laminated with the substrate. The substrate is laminated on one side or both sides of the thermally expandable fireproof sheet. The base material is usually a woven fabric or non-woven fabric, and the fibers used for the woven fabric or non-woven fabric are not particularly limited, but noncombustible materials or semi-incombustible materials are preferable, such as glass fiber, ceramic fiber, Cellulose fibers, polyester fibers, carbon fibers, graphite fibers, thermosetting resin fibers and the like are preferred.

Here, the noncombustible material is a material that does not burn for 20 minutes after the start of heating when heat from a normal fire is applied (Article 2, Item 9 of the Building Standards Law, Building Standards Law Enforcement Order No. 108 See Article 2, Item 1). Examples include carbon fiber, metal, and glass. A "quasi-noncombustible material" is a material that does not burn for 10 minutes after the start of heating when heated by a normal fire (see Article 1, Item 5 of the Enforcement Order of the Building Standards Law).

INDUSTRIAL APPLICABILITY The fire-resistant resin composition of the present invention and the fire-resistant resin molded article formed therefrom can be used to impart fire-resistant performance to building materials. Building materials include structures such as walls, floors, bricks, roofs, and plate materials; fittings such as windows (including double sliding windows, casement windows, double-hung windows, etc.), shoji screens, doors (that is, doors), sliding doors, and transoms; wiring , plumbing; and the like. The fire-resistant resin composition of the present invention and the fire-resistant resin molded article formed therefrom can be placed in these building materials to reduce or prevent the intrusion of fire and smoke. For example, as shown in FIG.
provides excellent fire and water resistance.

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. Production of thermally expandable fireproof sheets of Examples 1 to 34 and Comparative Examples 1 and 2 The compositions of Examples and Comparative Examples prepared according to the compositions shown in Tables 1 to 6 were kneaded with a kneading roll at 150°C for 8 minutes. Then, it was press-molded and cured to prepare a thermally expandable fireproof sheet having a thickness of 1.5 mm as a compact.
In addition, each raw material used for preparation of the composition is as follows.
[Matrix component]
PVC resin (product name: TK-1000, Shin-Etsu Chemical Co., Ltd., SP value: 9.5)
[Plasticizer]
Diisodecyl phthalate (product name: DIDP, Jplus Co., Ltd., SP value: 8.5
)
tricresyl phosphate (product name: TCP, Daihachi Chemical Co., Ltd., SP value: 9.7)
Trixylenyl phosphate (product name: TXP, Daihachi Chemical Co., Ltd.)
Cresyl diphenyl phosphate (product name: CDP, Daihachi Chemical Co., Ltd.)
2-ethylhexyldiphenyl phosphate (product name: #41, Daihachi Chemical Co., Ltd.)
Di-2-ethylhexyl phthalate (product name: DOP, Jplus Co., Ltd., SP value: 8.9)
[Metal material]
Zinc oxide (Product name: Type 1 zinc oxide, Sakai Chemical Industry Co., Ltd.)
Metal zinc (product name: zinc powder, grade: R powder, Hakusui Tech Co., Ltd.)
Zinc chloride (Product name: Zinc chloride, Hanwa Kogyo Co., Ltd.)
Iron chloride (Product name: Iron chloride, Sanko Shokai Co., Ltd.)
Ferrocene (Product name: Ferrocene, Tokyo Chemical Industry Co., Ltd.)
Iron oxide (product name: ferric oxide, Tetsugen Co., Ltd.)
Copper oxide (Product name: Copper oxide FCO-M6, Furukawa Chemicals Co., Ltd.)
[Inorganic filler]
Calcium carbonate (product name: Whiten BF-300, Bihoku Funka Kogyo Co., Ltd.)
[Phosphorus compound]
Melamine polyphosphate, melam, melem (product name: Phosmel (registered trademark) 200, Nissan Chemical Co., Ltd.)
Aluminum phosphite (product name: APA100, Taihei Kagaku Sangyo Co., Ltd.)
Ammonium polyphosphate (product name: AP422, Clariant Chemicals)
Melamine-coated ammonium polyphosphate (product name: AP462, Clariant Chemicals)
Melamine polyphosphate (product name: MPP-A, Sanwa Chemical Co., Ltd.)
[Thermal expandable graphite]
Thermally expandable graphite (product name: CA-60N, Air Water Inc.)
Thermally expandable graphite (product name: ADT351, ADT company, average aspect ratio: 21.3)

(Fire resistance test)
Made by Yoshino Gypsum Co., Ltd., reinforced gypsum board GB-F (thickness 12.5 mm) 910 mm × 910 mm
In the center above, each fireproof sheet (1.5 mm
Thickness, 300 mm × 300 mm) at 8 locations at intervals of 150 mm on the periphery of the sheet, 1 location at the center,
A total of 9 locations were attached with a staple gun. The obtained specimen was subjected to a fire resistance test for 20 minutes in a vertical furnace (heating perpendicular to the sample), adjusting the heating conditions according to the ISO heating curve. After the test for 20 minutes, the combustion residue of the refractory sheet can be retained without dropping.
The case where the surface layer was partly dropped although it was held, was rated as ◯, and the case where the surface layer was completely dropped was rated as x.

(Weight reduction rate)
Test pieces (length 50 mm,
Width 50 mm, thickness 1.5 mm) are immersed in 200 g of pure water and dried in a closed container at 60 ° C.
soaked for a week. After that, the test piece was taken out, and the pure water in which it was immersed was evaporated at 90° C. and dried. The weight of the deposit deposited from the test piece was measured, and the weight reduction rate was calculated by the following formula.
(Weight of deposit) / (Weight of test piece before immersion) x 100 (%)

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

For example, the configurations, methods, steps, shapes, materials, numerical values, etc. mentioned in the above-described embodiments and examples are merely examples, and different configurations, methods, steps, shapes,
Materials, numerical values, and the like may be used.

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

1: Thermally expandable fireproof sheet.

Claims (7)

one or more matrix components selected from the group consisting of vinyl chloride resins and chlorinated vinyl chloride resins;
a plasticizer;
thermally expandable graphite;
one or more metal materials selected from the group consisting of metallic zinc, zinc oxide, zinc chloride, iron chloride, ferrocene, iron oxide and copper oxide;
containing an inorganic filler,
The plasticizer has a compatibility parameter difference of greater than 0.5 calculated by the small method between the matrix component and the plasticizer, and the compatibility calculated by the small method between the matrix component and the plasticizer. A plasticizer with a parameter difference of 0.5 or less,
10 to 200 parts by weight of the thermally expandable graphite and 10 to 200 parts by weight of the total amount of the metal material and the inorganic filler with respect to 100 parts by weight of the matrix component ,
A fire-resistant resin composition, characterized in that the content of a water-soluble phosphorus compound in the fire-resistant resin composition is 10% by weight or less . 2. The fire-resistant resin composition according to claim 1, which contains substantially no water-soluble phosphorus compound. 3. The fire-resistant resin composition according to claim 1, wherein the content of said metal material in the fire-resistant resin composition is 0.1% by weight to 25% by weight. 4. The fire-resistant resin composition according to any one of claims 1 to 3 , wherein the thermally expandable graphite has an average aspect ratio of 20 or more. A fire-resistant resin molding made of the fire-resistant resin composition according to any one of claims 1 to 4 . A thermally expandable fireproof sheet comprising the fireproof resin composition according to any one of claims 1 to 4 . A fitting comprising the fire-resistant resin molding according to claim 5 or the thermally expandable fire-resistant sheet according to claim 6 .