JP2019189777A - Fire retardant resin composition, molded body and wound body - Google Patents

Abstract

To provide a fire retardant resin composition having good workability while maintaining excellent fire retardancy.SOLUTION: There is provided a fire retardant resin composition containing an epoxy resin, a heat expandable graphite, a phosphorus compound, and a liquid rubber, and preferably used in applications of a fire retardant coating material for a pillar, a beam, and a wall, applications in a fire retardant sash, applications of a fire retardant section penetration structure, and applications of a fire retardant door.SELECTED DRAWING: None

Description

  The present invention relates to a fireproof resin composition, a molded body, and a wound body.

  In the field of building materials, fire resistance has traditionally been important. In recent years, with the expansion of the use of resin materials, resin materials having fire resistance performance have been widely used as building materials.

  For example, Patent Document 1 discloses a refractory resin composition comprising 100 parts by mass of an epoxy resin, 10 to 300 parts by mass of thermally expandable graphite, and 50 to 500 parts by mass of an inorganic filler.

JP 2000-143941 A

  However, the fire-resistant resin composition of Patent Document 1 contains a large amount of inorganic filler that does not burn in order to impart fire resistance. For this reason, even if the fire resistance performance is good, the inorganic filler is in the form of a powder, so that the binding property of the fire resistant resin composition containing the filler is impaired, such as sheet formability or winding property of the fire resistant resin composition. There is a problem that workability is lowered.

  For example, if the refractory resin composition contains a large amount of powdered inorganic filler, it may be difficult to bend when formed into a long sheet, or it may be difficult to wind, Since it is easy to be cracked, wrinkled or marked, it may interfere with the mounting work on building materials such as sashes.

  In view of the above, an object of the present invention is to provide a fire resistant resin composition having good workability while maintaining excellent fire resistance.

  In order to achieve the above object, the present inventors have excellent fire resistance by further containing liquid rubber in a fire resistant resin composition containing an epoxy resin, thermally expandable graphite and a phosphorus compound. However, the present inventors have found that good workability can be obtained and have completed the present invention. That is, the present invention is as follows.

[1] A fire-resistant resin composition containing an epoxy resin, thermally expandable graphite, a phosphorus compound, and liquid rubber.
[2] The fire resistant resin composition according to [1], wherein the liquid rubber is polybutadiene.
[3] The fire resistant resin composition according to [1] or [2], further containing an inorganic filler.
[4] With respect to 100 parts by mass of the epoxy resin, 40 to 160 parts by mass of the thermally expandable graphite, 90 to 260 parts by mass of the total amount of the phosphorus compound and the inorganic filler, and 0. The fire resistant resin composition according to [3], which contains 01 to 110 parts by mass.
[5] Any one of [1] to [4] for use in a fireproof covering material for pillars, beams and walls, a fireproof sash, a fireproof section penetration structure, and a fireproof door The fire-resistant resin composition as described in 2.
[6] A molded article obtained by molding the fireproof resin composition according to any one of [1] to [5].
[7] The molded article according to [6], which is used for a fireproof covering material for a column, a beam, and a wall, a fireproof sash, a fireproof section penetration structure, and a fireproof door.
[8] The molded product according to [6] or [7], wherein the length in the longitudinal direction is 1 m or more.
[9] A wound body obtained by winding the refractory resin composition according to any one of [1] to [5].
[10] The wound body according to [9], which is used for a fireproof covering material for pillars, beams, and walls, a fireproof sash, a fireproof compartment penetration structure, and a fireproof door.

According to the present invention, it is possible to provide a fire resistant resin composition having good workability while maintaining fire resistance.
Since the fire-resistant resin composition of the present invention is excellent in fire resistance and workability, it can be attached to and wound around building materials such as sashes, and cracks and wrinkles occur when covering or sticking to a building or the like. The possibility of occurrence is low, and excellent fire resistance can be imparted.

  Hereinafter, although the embodiment which concerns on the fireproof resin composition of this invention, a molded object, and a wound body is described, this invention is not limited to these.

[1. Refractory resin composition]
The fire resistant resin composition according to the present embodiment contains an epoxy resin, thermally expandable graphite, a phosphorus compound, and liquid rubber. Here, the liquid rubber refers to a synthetic rubber having fluidity under the conditions of 20 ° C. and 1 atmosphere (1.01 × 10 ⁻¹ MPa).
It is presumed that the liquid rubber is compatible or mixed with the epoxy resin and can increase the flexibility and elongation when it is formed into a sheet or the like. As a result, workability such as sheet formability or wrapping property of the refractory resin composition can be improved.

  In addition, the fire resistance performance of the fire resistant resin composition according to the present embodiment is manifested when the two components of thermally expandable graphite and phosphorus compound exhibit their properties. Specifically, the heat-expandable graphite forms an expanded heat insulating layer during heating to prevent heat transfer. The phosphorus compound imparts shape retention ability to the expanded heat insulating layer and any inorganic filler.

(Liquid rubber)
Examples of the liquid rubber include diene rubbers, olefin rubbers, urethane rubbers, silicone rubbers, polysulfide rubbers, and fluorine rubbers, but diene rubbers are preferable.

  Examples of the diene rubber include styrene butadiene rubber, polyisoprene, polybutadiene, polychloroprene, acrylonitrile butadiene rubber, and the like.

  Among the diene rubbers, polybutadiene is preferable from the viewpoint of flexibility. Polybutadiene can further enhance the flexibility and elongation when it is formed into a sheet or the like due to the effect of the polybutadiene structure. The polybutadiene according to the present invention refers to various polybutadienes such as butadiene homopolymer, modified polybutadiene, and butadiene copolymer.

Examples of the modified polybutadiene include epoxy-modified polybutadiene, acid-modified polybutadiene, and terminal hydroxyl group-modified polybutadiene.
Among the above, the acid-modified component of the acid-modified polybutadiene is not particularly limited, and examples thereof include unsaturated carboxylic acids. As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride are preferable, maleic acid and maleic anhydride are preferable, and maleic acid is more preferable. Therefore, as the acid-modified polybutadiene, maleic acid-modified polybutadiene and maleic anhydride-modified polybutadiene are preferable.

  Examples of butadiene copolymers include butadiene / styrene / random copolymers. In addition, unmodified liquid polybutadiene can also be used.

The polybutadiene is preferably a low molecular weight and liquid polybutadiene, and the number average molecular weight (Mn) thereof is preferably 1400 to 8000, more preferably 1500 to 5000. In addition, the number average molecular weight of polybutadiene is measured by a gel permeation chromatography (GPC) method (polystyrene conversion).
The polybutadiene is preferably an epoxy-modified polybutadiene, or a maleic acid-modified polybutadiene that can impart flexibility by reacting with a hydroxyl group, an amine, or the like from the viewpoint of obtaining better workability.

  The content of the liquid rubber is not particularly limited, but if there is too much liquid rubber, the compounding ratio of the epoxy resin may decrease, and sufficient cohesive force cannot be obtained. Conversely, if there is too little liquid rubber, the refractory resin composition The flexibility of things may be insufficient. From this viewpoint, the content of the liquid rubber is preferably 0.01 to 110 parts by mass, more preferably 5 to 70 parts by mass, and 10 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin. Further preferred.

(Epoxy resin)
The epoxy resin used in the present embodiment is not particularly limited, but is basically obtained by reacting an epoxy compound having an epoxy group with a curing agent.
Specific examples of the epoxy compound include glycidyl ether type and glycidyl ester type. The glycidyl ether type may be bifunctional or may be trifunctional or more polyfunctional. The same applies to the glycidyl ester type. The epoxy compound may contain a monofunctional compound in order to adjust the degree of crosslinking. Among these, a bifunctional glycidyl ether type is preferable.

  Examples of the bifunctional glycidyl ether type epoxy compound include aliphatic glycols such as alkylene glycol types such as polyethylene glycol type and polypropylene glycol type, neopentyl glycol type, 1,6-hexanediol type, and hydrogenated bisphenol A type. An epoxy compound is illustrated. Furthermore, aromatic epoxy compounds containing aromatic rings such as bisphenol A type, bisphenol F type, bisphenol AD type, ethylene oxide-bisphenol A type, propylene oxide-bisphenol A type, and the like can be given. Among these, aromatic epoxy compounds such as bisphenol A type and bisphenol F type are preferable.

Examples of the glycidyl ester type epoxy compound include hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, and p-oxybenzoic acid type epoxy compounds.
Examples of the polyfunctional glycidyl ether type epoxy compound include a phenol novolak type, an orthocresol novolak type, a DPP novolak type, a dicyclopentadiene / phenol type, and the like.
These epoxy compounds may be used independently and 2 or more types may be used together.

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

Further, the epoxy resin may be provided with flexibility. In order to impart flexibility, the following method is used.
(1) Increase the molecular weight between cross-linking points.
(2) Reduce the crosslinking density.
(3) Introducing a soft molecular structure.
(4) A plasticizer is added.
(5) Introducing an interpenetrating network (IPM) structure.
(6) Disperse and introduce rubber-like particles.
(7) Introducing microvoids.

The above (1) is a method in which at least one of an epoxy compound and a curing agent is used in advance with a long molecular chain, and these are reacted to increase the distance between cross-linking points and develop flexibility. . For example, a polyether diamine such as polypropylene diamine may be used as a curing agent.
(2) is a method of expressing flexibility by reducing the cross-linking density in a certain region by reacting at least one of an epoxy compound and a curing agent with those having a small functional group. For example, a bifunctional amine or a monofunctional epoxy compound may be used as at least a part of the epoxy compound as a curing agent.
(3) is a method of developing flexibility using a compound having a soft molecular structure in at least one of an epoxy compound and a curing agent. For example, a heterocyclic diamine may be used as a curing agent, or an alkylene glycol glycidyl ether or the like may be used as an epoxy compound.

(4) is a method of adding a plasticizer to the refractory sheet as a non-reactive diluent.
(5) is a method of expressing flexibility with an interpenetrating network (IPN) structure in which a resin having another soft structure is introduced into the crosslinked structure of the epoxy resin.
(6) is a method of blending and dispersing liquid or granular rubber particles in an epoxy resin matrix.
(7) is a method of expressing flexibility by introducing microvoids of 1 μm or less into an epoxy resin matrix.

(Thermally expandable graphite)
Although the said thermally expansible graphite expand | swells at the time of a heating, what differs in the thermal expansion start temperature can be obtained as a commercial item.
Thermally expandable graphite is a conventionally known substance, which is obtained by treating a powder such as natural scaly graphite, pyrolytic graphite, or quiche graphite with an inorganic acid and a strong oxidizing agent to produce a graphite intercalation compound. It is a kind of crystalline compound that maintains the layered structure of carbon. Examples of the inorganic acid include concentrated sulfuric acid, nitric acid, selenic acid, and the like, and examples of the strong oxidizing agent include hydrogen peroxide.

  The heat-expandable graphite obtained by acid treatment as described above is preferably further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like. Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine. Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium, and magnesium, oxides, carbonates, sulfates, and organic acid salts.

The thermal expandable graphite preferably has a particle size in the range of 20 to 200 mesh. When the particle size is 20 mesh or more, the degree of expansion of graphite is large, and a sufficient expansion residue is easily obtained. Further, when the particle size is 200 mesh or less, it has an advantage that the degree of expansion of graphite is large, and has good dispersibility when kneaded with the epoxy resin, and it is easy to maintain physical properties. Examples of commercially available neutralized thermally expandable graphite include “GRAFGUARD # 160”, “GRAFGUARD # 220” manufactured by UCAR CARBON, “GREP-EG” manufactured by Tosoh Corporation, and the like.
From the viewpoint of facilitating the formation of the expanded heat insulating layer, the thermally expandable graphite is preferably 40 to 160 parts by mass and more preferably 45 to 155 parts by mass with respect to 100 parts by mass of the epoxy resin.

(Phosphorus compound)
It does not specifically limit as a phosphorus compound, For example, various phosphoric acid esters, such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, PX-200 ( Condensed phosphate ester derived from bisphenol A such as Daihachi Chemical Industry Co., Ltd., CR-733S (produced by Daihachi Chemical Industry Co., Ltd.), Condensed phosphate ester derived from xylenol such as CR-741S (produced by Daihachi Chemical Industry Co., Ltd.) Condensed phosphoric acid esters such as the above, halogen-containing phosphoric acid esters containing halogen such as chlorine in the structure of the above-mentioned phosphoric acid esters and condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters, sodium phosphate, phosphoric acid Metal phosphates such as potassium, magnesium phosphate, aluminum phosphate Metal phosphites such as sodium phosphite and aluminum phosphite, ammonium polyphosphates, aluminum polyphosphates, melamine polyphosphate, melam polyphosphate, melem polyphosphate, lower phosphate, represented by the following formula (1) And the like.

In formula (1), R ¹ and R ³ are the same or different and each represents hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon. The aryloxy group of Formula 6-16 is shown.

The said phosphorus compound can use 1 type, or 2 or more types.
Among these, from the viewpoint of fire resistance, red phosphorus, the compound represented by the above formula (1), and ammonium polyphosphates are preferable, and ammonium polyphosphates are more preferable in terms of performance, safety, cost, and the like. preferable.

  Examples of the compound represented by the above formula (1) include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, and 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, diethyl Examples thereof include phenylphosphinic acid, diphenylphosphinic acid, and bis (4-methoxyphenyl) phosphinic acid. Among them, t-butylphosphonic acid is preferable in terms of high flame retardancy although it is expensive.

  The ammonium polyphosphates are not particularly limited. For example, ammonium polyphosphate, melamine-modified ammonium polyphosphate, ammonium polyphosphate, piperazine polyphosphate, ammonium polyphosphate, and melamine and / or as a foaming agent for the above-mentioned ammonium polyphosphates. Although the thing which added pentaerythritol etc. is mentioned, Ammonium polyphosphate is preferable from points, such as a flame retardance, safety | security, cost, and handleability. Examples of commercially available products include “trade name: EXOLIT AP422” and “trade name: EXOLIT AP462” manufactured by Clariant.

  It is considered that the phosphorus compound reacts with metal carbonates such as calcium carbonate and zinc carbonate to promote the expansion of the metal carbonate. In particular, when ammonium polyphosphate is used as the phosphorus compound, a high expansion effect is obtained. can get. It also acts as an effective aggregate and forms a highly shape-retaining residue after combustion.

  From the viewpoint of shape retention, the phosphorus compound is preferably 90 to 260 parts by mass, and more preferably 95 to 255 parts by mass with respect to 100 parts by mass of the epoxy resin.

(Inorganic filler)
It is preferable that the refractory resin composition according to the present embodiment further contains an inorganic filler. The inorganic filler is an inorganic substance excluding the above-described thermally expandable graphite and phosphorus compound, such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite. Hydrous minerals such as metal oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, especially metal hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate Metal carbonates such as inorganic phosphate, calcium sulfate, gypsum fiber, calcium silicates such as calcium silicate, silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay , Sepiolite, imogolite, sericite, Glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, Examples include zinc stearate, calcium stearate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dewatered sludge.
These inorganic fillers can be used alone or in combination of two or more. In addition, the said metal oxide, the said water-containing inorganic substance, metal carbonate, the said calcium salt, etc. and the compound containing a metal element and another element are called a metal compound.

  The inorganic filler preferably plays an aggregate role and contributes to an improvement in the strength of expansion residue generated after heating and an increase in heat capacity.

  Specifically, in addition to calcium carbonate, metal carbonates typified by zinc carbonate, titanium oxide that plays an aggregate role, metal oxides such as zinc oxide, and an aggregate role, it gives an endothermic effect during heating. Water-containing inorganic substances represented by aluminum hydroxide, magnesium hydroxide and the like are preferable. Among them, it is more preferable to use a metal carbonate or metal oxide because of its high effect as an aggregate, and it is more preferable to use calcium carbonate, zinc carbonate, titanium oxide, zinc oxide, or silicon oxide. Most preferred.

  When the inorganic filler used in the present invention is granular, the average particle diameter is preferably in the range of 0.5 to 200 μm, more preferably in the range of 1 to 50 μm. The average particle diameter can be measured by an air permeation method.

  When the amount of the inorganic filler added is small, the dispersibility largely affects the performance, so that the average particle size is small, but secondary aggregation can be prevented when the average particle size is 0.5 μm or more. It is possible to prevent the sex from becoming worse.

  Moreover, when there is much addition amount of an inorganic filler, as high filling progresses, the viscosity of a resin composition becomes high and a moldability falls. However, since the viscosity of the resin composition can be lowered by increasing the particle diameter, those having a larger particle diameter are preferable among the above ranges. In addition, if an average particle diameter is 200 micrometers or less, it can prevent that the surface property of a molded object and the mechanical physical property of a resin composition fall.

  Examples of commercially available products of the above-mentioned water-containing inorganic materials include aluminum hydroxide, “trade name: Hygielite H-42M” (manufactured by Showa Denko KK) having an average particle diameter of 1 μm, and “trade name: Hygilite H having an average particle diameter of 18 μm. -31 "(manufactured by Showa Denko KK) and the like. Examples of the commercial products of calcium carbonate include “trade name: Whiten SB red” (manufactured by Shiraishi Calcium Co., Ltd.) having an average particle size of 1.8 μm, and “trade name: BF300” (Bihoku Powder Co., Ltd.) having an average particle size of 8 μm. Manufactured) and the like.

From the viewpoint of improving the strength of the expansion residue generated after heating and increasing the heat capacity, the inorganic filler is preferably 20 to 160 parts by mass and preferably 25 to 155 parts by mass with respect to 100 parts by mass of the epoxy resin. Is more preferable.
In addition, on the assumption that the phosphorus compound is contained, the total amount of the phosphorus compound and the inorganic filler is preferably 90 to 260 parts by mass.

  Moreover, in this embodiment, by combining thermally expandable graphite and a phosphorus compound, scattering of thermally expandable graphite during combustion can be suppressed and shape retention can be achieved. If there is too much heat-expandable graphite, the graphite expanded at the time of combustion will be scattered, and a sufficient heat-insulating layer will not be obtained at the time of heating. Conversely, if there is too much phosphorus compound, the heat-insulating layer will not be sufficient and the desired effect will be achieved. It becomes difficult to obtain. Therefore, the mass ratio of thermally expandable graphite and phosphorus compound is preferably thermally expandable graphite: phosphorus compound = 10: 3 to 10:60, more preferably 10: 5 to 10:55, Preferably it is 10: 7-10: 50.

  From the viewpoint of shape retention during combustion, the range of thermally expandable graphite: phosphorus compound = 10: 5 to 10:50 is excellent. Even if the composition itself is flame retardant, if the shape retainability is insufficient, the brittle residue collapses and penetrates the flame, so depending on whether the shape retainability is sufficient, Application forms vary greatly.

  Furthermore, in the present embodiment, as long as the purpose is not impaired, as necessary, in addition to antioxidants such as phenol-based, amine-based, sulfur-based and the like, metal harm-preventing agents, antistatic agents, stabilizers, crosslinking agents. , Lubricants, softeners, pigments, tackifier resins, additives such as molding aids, and tackifiers such as petroleum resins.

Next, the manufacturing method of the fireproof resin composition which concerns on this embodiment is demonstrated.
Examples of the production method include suspending an epoxy compound, a curing agent, a thermally expandable graphite, a phosphorus compound, a liquid rubber, an inorganic filler, and the like, which are each raw material of the refractory resin composition, in an organic solvent, There is a method of heating and melting to form a paint. Moreover, the said refractory resin composition can be obtained by the method of disperse | distributing to an organic solvent and preparing a slurry, and the method of fuse | melting each said raw material under a heating. Especially, since the process of removing an organic solvent is unnecessary, it is preferable not to use an organic solvent.

  The fire-resistant resin composition is kneaded with the above raw materials using a known apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a reiki machine, and a planetary stirrer. Can also be obtained.

  When manufacturing the said refractory resin composition, it can knead | mix separately with the unreacted component and epoxy curing agent of an epoxy resin, and knead | mixing with a static mixer, a dynamic mixer, etc. just before shaping | molding.

[2. Molded body and wound body]
The molded body according to this embodiment is formed by molding a refractory resin composition. The said molded object can be manufactured by shape | molding a refractory resin composition. Molding includes press molding, extrusion molding, injection molding, and roll molding. When the fireproof resin composition is formed into a sheet shape, the thickness of the sheet is not particularly limited, but is preferably 0.2 to 10 mm. Moreover, it is preferable that the said sheet | seat is elongate, it is preferable that the length of a longitudinal direction is 1 m or more, and it is more preferable that it is 2-400 m. In this case, the sheet width is preferably 0.005 to 2.0 m.

  Moreover, the wound body according to the present embodiment is formed by winding a refractory resin composition. The wound body is obtained by kneading the fire-resistant resin composition using a known device, forming it by a known molding method to obtain a fire-resistant sheet, and winding this as a wound body with a winding roll. Obtainable. The wound body also preferably has a length in the longitudinal direction of 1 m or more, and the sheet width in this case is preferably 0.005 to 2.0 m.

The fireproof resin composition, the molded body, and the wound body according to the present embodiment as described above are respectively used as a fireproof covering material for a column, a beam, and a wall, a use of a fireproof sash, a use of a fireproof compartment penetration part structure, In addition, it is preferably used for fire door applications.
In addition, “fire prevention zone” is a general building and is an effective fire prevention zone that is separated by walls, floors, fire doors, etc. of semi-refractory structure in order to prevent the spread of fire and the spread of smoke in the event of a fire. Say. When a cable penetrates the wall or floor of this fire prevention compartment, fire prevention measures are also required for the penetration part.

  In addition to the above, fires are placed on walls such as windows (including sliding windows, open windows, raised and lowered windows, etc.), shoji, doors (ie doors), doors, bran and other fixtures, pillars, steel concrete, etc. And the intrusion of smoke can be reduced or prevented.

  Hereinafter, the present invention will be described in detail based on examples. In addition, this invention is not limited at all by the following examples.

1. Production of fireproof resin composition The materials shown in Table 1 below were prepared. Details of each of these materials are as follows. In addition, the unit of each table | surface is a mass part.

(1) Epoxy compound bisphenol F type epoxy compound ("E807" manufactured by Yuka Shell)
(2) Hardener hexamethylenediamine derivative ("FL052" manufactured by Mitsubishi Chemical Corporation)
(3) Thermally expandable graphite Thermally expandable graphite (“GREP-EG” manufactured by Tosoh Corporation)
(4) Phosphorus compound ammonium polyphosphate (“AP-422” manufactured by Clariant)
(5) Inorganic filler calcium carbonate ("BF-300" manufactured by Bihoku Flourishing Co., Ltd.)

(6) Polybutadiene A-1: Epoxy-modified polybutadiene (“Ricon 657” manufactured by Clay Valley)
A-2: Maleic acid-modified polybutadiene (“Ricon 130MA13” manufactured by Clay Valley)
A-3: Terminal hydroxyl group-modified liquid polybutadiene (“Krasol LBH-P2000” manufactured by Clay Valley)
A-4: Butadiene / styrene / random copolymer (Ricon 181 manufactured by Clay Valley)
A-5: Butadiene homopolymer (“Ricon 131” manufactured by Clay Valley)

(Example 1)
In accordance with the composition shown in Table 1, 40 parts by mass of an epoxy compound, 60 parts by mass of a curing agent, 100 parts by mass of thermally expandable graphite, 150 parts by mass of ammonium polyphosphate, 30 parts by mass of calcium carbonate, and 20 parts by mass of epoxy-modified polybutadiene were mixed with planetary agitation. The refractory resin composition was obtained by feeding to a machine and kneading.

The obtained refractory resin composition is sandwiched between polyethylene terephthalate sheets so as to have a size of 25 cm × 25 cm × 1.5 mm, and heated at 40 ° C. for 30 seconds to form a refractory resin composition sheet. Produced.
The refractory resin composition sheet was cured by heating in an oven at 90 ° C. for 24 hours, and the refractory resin composition sheet of Example 1 was produced.

(Example 2)
A refractory resin composition sheet of Example 2 was produced in the same manner as in Example 1 except that 20 parts by mass of the epoxy-modified polybutadiene was changed to 0.1 parts by mass.

(Example 3)
A refractory resin composition sheet of Example 3 was produced in the same manner as in Example 1 except that 20 parts by mass of the epoxy-modified polybutadiene was changed to 100 parts by mass.

Example 4
A refractory resin composition sheet of Example 4 was produced in the same manner as in Example 1 except that 0.1 part by mass of maleic acid-modified polybutadiene was used in place of the epoxy-modified polybutadiene.

(Example 5)
A refractory resin composition sheet of Example 5 was produced in the same manner as in Example 1 except that 20 parts by mass of maleic acid-modified polybutadiene was used instead of epoxy-modified polybutadiene.

(Example 6)
A refractory resin composition sheet of Example 6 was produced in the same manner as in Example 1 except that 100 parts by mass of maleic acid-modified polybutadiene was used in place of the epoxy-modified polybutadiene.

(Example 7)
A refractory resin composition sheet of Example 7 was produced in the same manner as Example 1 except that 20 parts by mass of terminal hydroxyl group-modified liquid polybutadiene was used instead of epoxy-modified polybutadiene.

(Example 8)
A refractory resin composition sheet of Example 8 was produced in the same manner as in Example 1 except that 20 parts by mass of butadiene / styrene / random copolymer was used in place of the epoxy-modified polybutadiene.

Example 9
Example 1 is performed in the same manner as in Example 1 except that 100 parts by mass of thermally expandable graphite is changed to 50 parts by mass, 150 parts by mass of ammonium polyphosphate is changed to 250 parts by mass, and 30 parts by mass of calcium carbonate is not included. 9 fire-resistant resin composition sheets were prepared.

(Example 10)
Example 10 is the same as Example 1 except that 100 parts by mass of thermally expandable graphite is changed to 50 parts by mass, 150 parts by mass of ammonium polyphosphate is changed to 100 parts by mass, and 30 parts by mass of calcium carbonate is not included. A fire resistant resin composition sheet was prepared.

(Example 11)
Compared to the case of Example 1, except that 100 parts by mass of thermally expandable graphite is changed to 150 parts by mass, 150 parts by mass of ammonium polyphosphate is changed to 250 parts by mass, and 30 parts by mass of calcium carbonate is not included. The experiment was conducted in exactly the same manner as in Example 1 to produce the fire resistant resin composition sheet of Example 11.

(Example 12)
Example 1 is performed in the same manner as in Example 1 except that 100 parts by mass of thermally expandable graphite is changed to 150 parts by mass, 150 parts by mass of ammonium polyphosphate is changed to 100 parts by mass, and 30 parts by mass of calcium carbonate is not included. Twelve refractory resin composition sheets were prepared.

(Example 13)
A refractory resin composition sheet of Example 13 was produced in the same manner as in Example 1 except that 100 parts by mass of butadiene homopolymer was used instead of epoxy-modified polybutadiene.

(Comparative Example 1)
A refractory resin composition sheet of Comparative Example 1 was produced in the same manner as Example 1 except that it did not contain epoxy-modified polybutadiene.

(Comparative Example 2)
Except for epoxy-modified polybutadiene, the amount of ammonium polyphosphate used was changed from 150 parts by weight to 100 parts by weight, and the amount of calcium carbonate used was changed from 30 parts by weight to 150 parts by weight. Thus, a fire resistant resin composition sheet of Comparative Example 2 was produced.

(Comparative Example 3)
Except for epoxy-modified polybutadiene, the amount of ammonium polyphosphate used was changed from 150 parts by weight to 125 parts by weight, and the amount of calcium carbonate used was changed from 30 parts by weight to 100 parts by weight. Thus, a fire resistant resin composition sheet of Comparative Example 3 was produced.

2. Evaluation of each fireproof resin composition sheet About the fireproof resin composition sheet | seat of said Examples 1-13 and Comparative Examples 1-3, fire resistance and a softness | flexibility were evaluated as follows. The results are shown in Tables 1 to 3 below.

[Fire resistance evaluation]
<Shape retention>
A test piece of 98 mm × 98 mm and a thickness of 1.5 mm was cut out from the fireproof resin composition sheet, and the test piece was heated in an electric furnace at 600 ° C. for 30 minutes. ◯ when the shape of the test piece is maintained after heating, ◎ when the shape is held even when the test piece is heated upside down, and after heating, the shape of the test piece is not retained and collapses The case was evaluated as x.
In addition, if the test piece after heating has sufficient shape retaining property, this makes the resin composition itself difficult to burn, and makes it difficult for the flame to pass through the resin composition. It will have fire resistance.

<Expandable>
A test piece of 98 mm × 98 mm and a thickness of 1.5 mm was cut out from the fireproof resin composition sheet, and the test piece was heated in an electric furnace at 600 ° C. for 30 minutes. After heating, when the thickness of the test piece is 30 mm or more (expansion magnification calculated by the following method is 20 times or more), the thickness of the test piece is 15 mm or more and less than 30 mm (expansion magnification is 10 times or more and less than 20 times). In the case of ◯, the case where the thickness of the test piece was less than 15 mm (expansion magnification was less than 10 times) was evaluated as x.
In addition, if the test piece after a heating is fully expanded, the gap can be filled with the volume of the test piece, and the flame is more difficult to permeate. As a result, it has good fire resistance.
Calculation method of expansion ratio: Expansion ratio = thickness after heating ÷ thickness before heating

[Flexibility evaluation]
<Sheet formability>
The appearance of the refractory resin composition sheet immediately after production in each of the above examples was visually observed and evaluated as follows.
A: No cracks, etc., smooth surface B: No cracks, etc., but slightly rough surface C: Cracks, wrinkles, cracks present

<Workability>
Each refractory resin composition sheet of each of the examples and comparative examples was wound around a roller having a diameter of 100 mm or 200 mm, and the ease of winding as workability was evaluated by the operator's sense, and the refractory resin composition wound around The cracks of the object sheet were observed and evaluated as follows.
A: Roller diameter is 100 mm and there are no cracks B: Roller diameter is 100 mm and there are cracks etc. Roller diameter is 200 mm and there are no cracks C: Roller diameter is 200 mm and there are cracks etc. ◯ or more, flexibility of B or more is required, more preferably fire resistance is ◎, and flexibility is A.

  From the viewpoint of preventing the spread of fire, the molded body of the refractory resin composition must retain its shape after heating and burning, and it is necessary to satisfy certain flexibility conditions from the viewpoint of producing a long sheet product. Since the molded body of the fireproof resin composition according to the present invention satisfies the above performance, it can be widely applied to joinery.

Claims (10)

  A fire resistant resin composition containing an epoxy resin, thermally expandable graphite, a phosphorus compound, and liquid rubber.   The refractory resin composition according to claim 1, wherein the liquid rubber is polybutadiene.   Furthermore, the fireproof resin composition of Claim 1 or 2 containing an inorganic filler.   40 to 160 parts by mass of the thermally expandable graphite, 90 to 260 parts by mass in total of the phosphorus compound and the inorganic filler, and 0.01 to 110 parts of the liquid rubber with respect to 100 parts by mass of the epoxy resin. The refractory resin composition according to claim 3, which is contained in parts by mass.   The use according to any one of claims 1 to 4 for use in fireproof coverings for pillars, beams and walls, fireproof sashes, fireproof compartment penetration structures, and fireproof doors. Fire resistant resin composition.   The molded object formed by shape | molding the refractory resin composition of any one of Claims 1-5.   The molded article according to claim 6, for use in fireproof coverings for pillars, beams and walls, fireproof sashes, fireproof compartment penetration structures, and fireproof doors.   The molded body according to claim 6 or 7, wherein the length in the longitudinal direction is 1 m or more.   The wound body formed by winding the fireproof resin composition of any one of Claims 1-5. The wound body according to claim 9, for use in fireproof coverings for pillars, beams and walls, fireproof sashes, fireproof compartment penetration structures, and fireproof doors.