JP2018035299A - Thermally expanded fire-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermally expanded fire-resistant resin composition having sufficient workability as well as sufficient fire-resisting properties.SOLUTION: A thermally expanded fire-resistant resin composition contains an epoxy resin (A), thermally-expandable graphite (B), an inorganic filler (C), and a flame retardant (D), the epoxy resin (A) being uncured.SELECTED DRAWING: None

Description

  The present invention relates to a thermal expansion refractory resin composition.

Conventionally, resin compositions having fire resistance have been used in building materials and the like.
In this type of resin composition, as fire resistance, in addition to the property that the material itself is difficult to burn when a fire occurs, the property that the generated flame does not pass through the material itself is also desired.

Therefore, a resin composition having such fire resistance has been proposed.
For example, a thermal expansion refractory resin composition that includes an epoxy resin, a phosphorus compound, thermal expansion graphite, and an inorganic filler and has thermal expansion and fire resistance has been proposed (Patent Document 1, etc.). .
According to this composition, it has flame retardancy, and the residue after combustion (burnt residue) has sufficient shape retention, so that the resin composition itself is difficult to burn, and the flame is the resin. It becomes difficult to pass through the composition, and as a result, it has the above fire resistance.

JP-A-11-116776

  However, with the thermal expansion refractory resin composition described in Patent Document 1, once it is formed into a predetermined shape, it is difficult to change to another shape, and the workability is good enough. hard. Moreover, when it is formed in a predetermined shape, it is difficult to use the surplus portion in another shape, and it is difficult to say that the workability is sufficient.

  In view of the above circumstances, an object of the present invention is to provide a thermal expansion refractory resin composition having not only sufficient fire resistance but also sufficient workability.

  As a result of intensive studies to solve the above problems, the present inventors have surprisingly used an uncured epoxy resin (A), which is made of thermally expandable graphite (B), inorganic filler (C ) And the flame retardant (D), it is easy to change to another shape even after it is once formed into a predetermined shape, and when it is formed into a predetermined shape, surplus The inventors have found that a thermal expansion refractory resin composition that can be easily formed into another shape can be obtained, and have completed the present invention.

That is, the thermal expansion refractory resin composition according to the present invention,
Epoxy resin (A),
Thermally expandable graphite (B);
An inorganic filler (C);
Containing a flame retardant (D),
The epoxy resin (A) is uncured.

According to this configuration, the thermal expansion refractory resin composition contains the uncured epoxy resin (A), the thermal expansion graphite (B), the inorganic filler (C), and the flame retardant (D). It has flame retardancy, and the residue after combustion (burnt residue) has sufficient shape retention, whereby the resin composition itself is difficult to burn, and the flame is difficult to pass through the resin composition. Therefore, it has sufficient fire resistance.
Here, when the thermally expanded refractory resin composition contains the cured epoxy resin (A), the curing is irreversible. There is a risk that it may be difficult to be deformed into a shape. Moreover, even if an excessive part is generated when it is formed into a predetermined shape, it may be difficult to form the excessive part into another shape.
However, since the epoxy resin (A) is uncured, once it is formed into a predetermined shape, it becomes easy to change to another shape, and when it is formed into a predetermined shape, surplus It is also easy to form this part in another shape. Therefore, compared with the case where the cured epoxy resin (A) is contained, the workability is excellent.
Therefore, the thermal expansion refractory resin composition has not only sufficient fire resistance but also sufficient workability.

In the thermal expansion refractory resin composition of the above configuration,
The flame retardant (D) may be an inorganic phosphorus compound.

  According to this structure, a flame retardant (D) can exhibit more flame retardance by being an inorganic phosphorus compound.

  ADVANTAGE OF THE INVENTION According to this invention, the thermal expansion refractory resin composition which has not only sufficient fire resistance but sufficient workability | operativity is provided.

  Embodiments of the present invention will be described below.

The thermal expansion refractory resin composition of this embodiment is
Epoxy resin (A),
Thermally expandable graphite (B);
An inorganic filler (C);
Containing a flame retardant (D),
The epoxy resin (A) is uncured.

The epoxy resin (A) imparts shape retention to the thermally expanded refractory resin composition in the event of a fire.
A conventionally well-known thing is mentioned as an epoxy resin (A).
Examples of the epoxy resin (A) include bisphenol A type, bisphenol B type, bisphenol F type, cresol type, and novolac type.
The epoxy resin (A) may be a liquid epoxy resin that is liquid at room temperature, or a solid epoxy resin that is solid at room temperature, or a mixture of these liquid epoxy resin and solid epoxy resin. There may be.

  The epoxy resin (A) is an uncured epoxy resin.

In the present embodiment, the fact that the thermal expansion refractory resin composition contains an uncured epoxy resin (A) means the following.
That is, the fact that the thermal expansion refractory resin composition contains an uncured epoxy resin (A) means that the hardness is determined according to JIS K6253-3: 2012 “vulcanized rubber and thermoplastic rubber-hardness. -When the ratio of the hardness after 5 seconds to the hardness after 1 second of the measurement is 20% or more when measured by the method of "Part 3: Durometer hardness", the thermal expansion refractory resin It means that the composition contains an uncured epoxy resin (A).
On the other hand, in the present embodiment, when the thermal expansion refractory resin composition contains the cured epoxy resin (A), contrary to the above, the hardness ratio is less than 20%. Means.

In the case where the epoxy resin (A) in an uncured state is contained, the curing agent (reactive curing agent) is not contained (that is, not used together with the curing agent), and the curing agent is contained (that is, the curing agent is not contained). The embodiment in combination with a curing agent may also be employed.
By containing the epoxy resin (A) in an uncured state, the material does not become a cured state even when heated at 120 ° C. or less during the production of the thermally expanded refractory resin composition, and is molded again. Is possible.

Among these, in an embodiment in which a curing agent is not used in combination, the epoxy resin (A) is in a state where the monomer is not polymerized because there is no curing agent capable of cross-linking (polymerizing) the monomer by reacting with the monomer. It has become. Moreover, it is not heated to 120 ° C. or higher, and the monomer is not self-polymerized. Moreover, in this case, it does not contain a hardening | curing agent means containing 5 mass parts or less of hardening | curing agents with respect to 100 mass parts of epoxy resins (A). That is, in addition to the case where no curing agent is contained, the curing agent that reacts with the epoxy resin (A) at less than 120 ° C. is contained in an amount of 5 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A). Is also included.
In addition, in the case of containing a curing agent in this way, the thermal expansion refractory resin composition (100% by mass) contains a curing agent of 1.25% by mass or less, and as described above, You may contain 5 mass parts or less of hardening | curing agents with respect to 100 mass parts of epoxy resins (A).

On the other hand, in an embodiment in which a curing agent is used in combination, the epoxy resin (A) has a curing agent that can react with the monomer to crosslink (polymerize) the monomer, but the monomer is not polymerized. It has become. In such a state, a curing agent that reacts with the monomer by being heated to 120 ° C. or more as a curing agent, but that does not react with the monomer even when heated at less than 120 ° C., that is, a latent curing agent is used. Can be formed.
Thus, the latent curing agent that does not cure the epoxy resin (A) even when used in combination with the epoxy resin (A) is mixed with the epoxy resin, based on JIS K7121: 2012 “Method for Measuring the Transition Temperature of Plastics”, When measured using a thermogravimetric and calorimetric apparatus (STA-6000, manufactured by PerkinElmer), Tg (glass transition temperature) is 150 ° C. or higher.
Examples of such latent curing agents include imidazole curing agents, tertiary amines, acid anhydrides or Lewis acid complex compounds.
In the embodiment where a curing agent is used in combination, as described above, the epoxy resin (A) is present in a state where the monomer is not self-polymerized.

The thermal expansion refractory resin composition contains the epoxy resin (A), so that it has flame retardancy, the residue after combustion (burn residue) has sufficient shape retention, and the flame is the resin. Since it becomes difficult to pass a composition, it has sufficient fire resistance.
In the state where the epoxy resin (A) is cured, the thermal expansion refractory resin composition exists in a relatively hard state in a state where a normal fire does not occur, and when a fire or the like occurs in this state, As described above, it has flame retardancy and shape retention, the resin composition itself is difficult to burn, and the flame is difficult to pass through the resin composition, so that it has sufficient fire resistance.
On the other hand, in the state where the epoxy resin (A) is not cured, the thermal expansion refractory resin composition exists in a relatively soft state in a state where a normal fire has not occurred, and when a fire or the like occurs in this state, The epoxy resin (A) is cured by heating due to fire, and as a result, has the flame retardancy and shape retention as described above, the resin composition itself is difficult to burn, and the flame is the resin composition. Therefore, it will have sufficient fire resistance.

Here, when the thermally expanded refractory resin composition contains the cured epoxy resin (A), the curing is irreversible. There is a risk that it may be difficult to be deformed into a shape. Moreover, even if an excessive part is generated when it is formed into a predetermined shape, it may be difficult to form the excessive part into another shape.
However, since the epoxy resin (A) is uncured, once it is formed into a predetermined shape, it becomes easy to change to another shape, and when it is formed into a predetermined shape, surplus It is also easy to form this part in another shape. Therefore, compared with the case where the cured epoxy resin (A) is contained, the workability is excellent.
Moreover, the thermal expansion refractory resin composition can have self-adhesiveness because the epoxy resin (A) is uncured. That is, the thermal expansion refractory resin composition of the present embodiment may have self-adhesiveness.

The compounding amount of the epoxy resin (A) is preferably 10 to 35% by mass and more preferably 20 to 30% by mass in the thermally expanded refractory resin composition (100% by mass).
When the blending amount is 10% by mass or more, there is an advantage that the shape retention of the combustion residue is excellent and the fire resistance can contribute.
By the said compounding quantity being 35 mass% or less, there exists an advantage that the compounding balance with another component becomes better.
As described above, the epoxy resin (A) may contain a liquid epoxy resin and a solid epoxy resin, and in this case, the ratio is not particularly limited. It is preferable that the content is larger than that of the solid epoxy resin. That is, the ratio (mass ratio) of the liquid epoxy resin to the solid epoxy resin is preferably 1 for the liquid epoxy resin to 1 for the solid epoxy resin. Further, the liquid epoxy resin is more preferably 4 or more and more preferably 5 or more with respect to 1 for the solid epoxy resin.
In addition, the direction in which an epoxy resin (A) contains only a liquid epoxy resin is more preferable than the case where a liquid epoxy resin and a solid epoxy resin are contained.

It is preferable that the compounding quantity of an above-described latent hardening | curing agent is 0-5 mass% with respect to a thermal expansion refractory resin composition (100 mass%).
Here, when the blending amount of the latent curing agent increases, a sufficient cured product tends to be formed at the time of combustion, whereas when it decreases, the composition tends to be excellent in long-term stability.
Considering this viewpoint, the blending amount of the latent curing agent is more preferably 2 to 3% by mass.

The thermally expandable graphite (B) imparts thermal expandability to the expanded refractory resin composition.
Examples of the thermally expandable graphite (B) include conventionally known powdery ones.
Examples of the thermally expandable graphite (B) include graphite such as natural scaly graphite, pyrolytic graphite, and cache graphite, and those obtained by treating these graphites with a treating agent. Examples of the treatment agent include inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, and strong oxidizing agents such as concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, and hydrogen peroxide. Can be mentioned.

The compounding amount of the thermally expandable graphite (B) is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass in the thermally expanded refractory resin composition (100% by mass).
When the blending amount is 10% by mass or more, there is an advantage that the composition can impart more sufficient expansion for closing the space during combustion.
When the blending amount is 30% by mass or less, there is an advantage that the composition can retain its shape retention more sufficiently during combustion and can prevent excessive expansion.

The inorganic filler (C) is a filler for imparting a shape to the thermally expanded refractory resin composition.
Examples of the inorganic filler (C) include conventionally known powders.
Examples of the inorganic filler (C) include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, and water. Aluminum oxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawn night, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, Activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, carbon black, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, sulfur Magnesium, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powder, slag fibers, fly ash, and dewatered sludge, these surface treatments Hinto the like.

The compounding amount of the inorganic filler (C) is preferably 10 to 40% by mass and more preferably 20 to 30% by mass in the thermally expanded refractory resin composition (100% by mass).
When the blending amount is 10% by mass or more, there is an advantage that the fireproof reinforcing effect by the inorganic filler can be more sufficiently obtained.
By the said compounding quantity being 40 mass% or less, there exists an advantage that the compounding balance with another component is achieved more fully.

The flame retardant (D) is for imparting flame retardancy to the thermally expanded refractory resin composition.
Examples of the flame retardant (D) include conventionally known powders.
Examples of the flame retardant (D) include inorganic phosphorus compounds. The inorganic phosphorus compound is not particularly limited. For example, red phosphorus; various phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate; sodium phosphate Metal phosphates such as potassium phosphate and magnesium phosphate; ammonium polyphosphates and the like.
When the flame retardant (D) is an inorganic phosphorus compound, it can exhibit more flame retardancy.
In addition, when the metal carbonates such as calcium carbonate and zinc carbonate are used as the inorganic filler (C), thermal expansion is caused by reaction with the ammonium polyphosphate by using ammonium polyphosphate as the phosphorus compound. It is considered that the expansion of the porous graphite (B) is promoted. Moreover, an inorganic filler (C) can work as a more effective aggregate, and can form a residue having higher shape retention after combustion.
Here, a combination of bromine and antimony is also considered as the flame retardant (D). In this case, the flame retardancy tends to be exhibited mainly in the region where organic components are burned and gasified. On the other hand, when an inorganic phosphorus compound is used, the barrier property of the char layer, which is a combustion residue, is improved. That is, the organic component can exhibit flame retardancy in a solid state.

The blending amount of the flame retardant (D) is preferably 20 to 40% by mass and more preferably 25 to 35% by mass in the thermally expanded refractory resin composition (100% by mass).
There exists an advantage that a combustion residue can be made stronger by the said compounding quantity being 20 mass% or more.
When the blending amount is 40% by mass or less, there is an advantage that a blending balance with other components, particularly a blending balance with the heat-expandable graphite (B) can be achieved.

In addition to the above, the thermal expansion refractory resin composition of the present embodiment may contain additives.
Examples of such additives include additives capable of imparting self-adhesiveness to the thermally expanded refractory resin composition; phenol fibers; resin microballoons; wetting and dispersing agents; thermal stabilizers; lubricants; vulcanization accelerators; Stabilizers; phenolic, amine-based, sulfur-based antioxidants; phenolic adhesives; petroleum resin-based adhesives; organic bentonites (thickeners); antifoaming agents; Non-reacting plasticizer; coupling agent; incombustible fiber; metal harm-preventing agent; antistatic agent; stabilizer; cross-linking agent; softener;

Among these additives, examples of the additive capable of imparting self-adhesiveness to the thermally expanded refractory resin composition include a rubber component and a thermoplastic elastomer component (E).
The rubber component or thermoplastic elastomer component (E) can be used in combination with the epoxy resin (A) to impart self-adhesiveness to the thermally expanded refractory resin composition.
Moreover, the fire resistance of a thermal expansion refractory resin composition can be improved.

Here, self-adhesiveness refers to a sheet-like composition of two sheets (50 mm width × 100 mm length × 5 mm thickness), as shown in the examples described later, and using a tensile tester. When the peel strength at the bonding interface in the 180-degree direction of the two sheet-like compositions is measured, it means a property that the base material is destroyed by exceeding the cohesive force of each sheet-like composition. Moreover, even when the base material is not destroyed when the peel strength is measured, the composition (50 mm width × 100 mm length × 1 mm thickness) is applied to the mounting panel in accordance with JIS Z0237: 2009 “13 Holding power”. A test plate made of SUS (25 mm width × 150 mm length × 2 mm thickness) was laminated so that a region (one region) of 25 mm width × 100 mm length of the composition was covered thereon, 30 When the load of 200 g was lowered at the end of the test plate that was not bonded to the composition in an environment of 0 ° C., there was no deviation between the test plate and the composition after 1 hour, and there was no drop. Means no nature.
Moreover, it is preferable that the thermal expansion refractory resin composition can maintain adhesiveness without causing bleed of the liquid material over time when stored for a long period of time.

  Thus, the thermal expansion refractory resin composition is more excellent by containing the epoxy resin (A) and the rubber component or the thermoplastic elastomer component (E). It will be self-adhesive.

  Examples of the rubber component or the thermoplastic elastomer component (E) include those having compatibility with the epoxy resin. Here, having compatibility with the epoxy resin (A) means that the epoxy resin (A) and the rubber component or the thermoplastic resin according to the oil retention test method defined in JIS A5751: 1995 “Oil building caulking material for building”. After holding the elastomer component (E) at 70 ° C. for 24 hours, the penetration width into a filter paper having a diameter of 11 cm corresponding to two types stipulated in JIS P3801: 1995 “filter paper (for chemical analysis)” is 10 mm or less. It means that the number of sheets indicates 3 or less.

Thus, when the rubber component or the thermoplastic elastomer component (E) is compatible with the epoxy resin (A), the rubber component or the thermoplastic elastomer component (E) is more easily dispersed in the epoxy resin (A). As a result, the region where the rubber component or thermoplastic elastomer component (E) and the epoxy resin (A) are present together and can exhibit self-adhesiveness is more evenly distributed in the thermally expanded refractory resin composition. Therefore, the self-adhesiveness is more easily exhibited.
Further, when the rubber component or the thermoplastic elastomer component (E) having compatibility with the epoxy resin (A) is contained, it is equivalent to the case of using the epoxy resin cured by a chemical reaction with a curing agent. Shape retention can be obtained.

The rubber components include natural rubber (NR), isoprene rubber (IR), butyl rubber (IIR), ethylene-propylene rubber (EPT, EPDM), butadiene rubber (BR), nitrile rubber (NBR), and styrene-butadiene rubber (SBR). ), Chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM), epchlorohydrin rubber (CO, ECO), silicone rubber (VMQ), fluoro rubber (FKM), urethane rubber (U), Examples thereof include polysulfide rubber (T) and liquids thereof, hydrogenated products, modified products, and the like.
Examples of the highly compatible rubber component include butyl rubber (IIR), nitrile rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), acrylic rubber (ACM) liquid, hydrogenated products, Examples include modified products.
Here, in particular, NBR (nitrile rubber) has a relatively high compatibility with the uncured epoxy resin (A). Also, in a system that does not contain a curing agent, NBR is extruded due to the crosslinking reaction of the curing agent because the curing agent does not exist in the first place even after undergoing a chemical reaction with the curing agent, such as heating during production. It is difficult for problems such as phase separation to occur. Therefore, such phase separation is difficult, and in combination with self-polymerization, it has high shape retention during combustion. Due to the high shape retention, the composition has a high barrier property and functions to delay the spread of flame.
On the other hand, in a system where a latent curing agent is present, NBR is liable to cause phase separation associated with heat polymerization and hardly contributes to shape retention as described above, but the latent curing agent and epoxy monomer are chemically combined during combustion. Since the polymer is formed by the reaction, it becomes a composition having high shape retention during combustion, which is equivalent to a system in which no curing agent is present.

Examples of the thermoplastic elastomer component include styrene elastomers, olefin elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers and derivatives thereof.
Moreover, what has a reactive functional group in the molecular terminal or molecular chain of the said component can be used as a thermoplastic elastomer component which has the said compatibility. Examples of the reactive functional group include a hydroxyl group, a silanol group, a carboxyl group, an isocyanate group, an acrylic group, a methacryl group, a vinyl group, and the like. By having these reactive functional groups in the molecular terminal or molecular chain, , Compatibility with epoxy resin is improved.

The compounding amount of the rubber component or the thermoplastic elastomer component (E) is preferably 2 to 15% by mass in the thermally expanded refractory resin composition (100% by mass), and preferably 3 to 8% by mass. More preferred.
When the blending amount is 2% by mass or more, there is an advantage that it can contribute to normal shape retention of the uncured epoxy resin (A).
When the blending amount is 15% by mass or less, there is an advantage that phase separation becomes difficult and a blending balance with other components can be obtained.

Among the above additives, as a plasticizer that does not chemically react with the other components in the composition (non-reactive plasticizer), a phenol PO addition plasticizer (for example, ED-508 (manufactured by ADEKA), styrenated phenol) Type plasticizer (for example, ED-512X (manufactured by ADEKA), di (2-ethylhexyl) dioctyl phthalate (DOP, for example, DOP (manufactured by Daihachi Chemical)), diisononyl phthalate (DINP, for example, DINP) (Made by Daihachi Chemical Co., Ltd.)).
The amount of such a non-reactive plasticizer is preferably 10 to 25% by mass, more preferably 15 to 20% by mass in the thermally expanded refractory resin composition (100% by mass).
Since the said compounding quantity is 10-25 mass%, since the softness | flexibility of a composition can be improved, workability | operativity can improve more.

According to the thermal expansion refractory resin composition of the present embodiment, it contains an uncured epoxy resin (A), thermal expansion graphite (B), an inorganic filler (C), and a flame retardant (D). Thus, the thermal expansion refractory resin composition has flame retardancy, and the residue after combustion (burn residue) has sufficient shape retention, whereby the resin composition itself is difficult to burn, Since it becomes difficult for a flame to pass through this resin composition, it has sufficient fire resistance.
Here, when the thermally expanded refractory resin composition contains the cured epoxy resin (A), the curing is irreversible. There is a risk that it may be difficult to be deformed into a shape. Moreover, even if an excessive part is generated when it is formed into a predetermined shape, it may be difficult to form the excessive part into another shape.
However, since the epoxy resin (A) is uncured, once it is formed into a predetermined shape, it becomes easy to change to another shape, and when it is formed into a predetermined shape, surplus It is also easy to form this part in another shape. Therefore, compared with the case where the cured epoxy resin (A) is contained, the workability is excellent.
Therefore, the thermal expansion refractory resin composition has not only sufficient fire resistance but also sufficient workability.

  Specifically, the fire resistance during combustion includes epoxy resin (A), thermally expandable graphite (B) (including those that have not been neutralized), and inorganic fillers (C ) Is expressed by exerting the properties of each component. More specifically, the heat-expandable graphite (B) forms an expanded heat insulating layer during heating by combustion to prevent heat transfer. At that time, the epoxy resin (A) used as the resin component forms a carbonized layer and functions as an expanded heat insulating layer. In addition, while it is accompanied by combustion decomposition by the curing agent activated by heating or by the epoxy monomer itself, on the other hand, a crosslinked structure is formed by polymerizing the epoxy monomer, so that shape retention after thermal expansion is achieved. It will be even better. The inorganic filler (C) has a function of increasing the heat capacity during heating, and the flame retardant (D) further improves the shape retention of the expanded heat insulating layer. Epoxy resin (A), like polyethylene, starts to thermally decompose with weight reduction from the 200 ° C. range, but tends to remain as a solid hydrocarbon compound and can greatly contribute to fire resistance.

  The thermal expansion refractory resin composition of the present embodiment includes, for example, an epoxy resin (A), a thermal expansion graphite (B), an inorganic filler (C), a flame retardant (D), and as necessary. By melt-kneading other additives with a known kneading apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a two-roller, a raker, a planetary stirrer, Can be obtained. The obtained composition can be formed into a fire-resistant sheet such as a sheet by a conventionally known molding method such as press molding, extrusion molding, or calendar molding. Moreover, when it contains a rubber component or a thermoplastic elastomer component (E), it can be formed into an adhesive fireproof sheet such as a sheet.

  The thermal expansion fire-resistant resin composition of this embodiment can be effectively used for building materials, buildings, ships, aviation, automobiles, machine tools, and the like. Further, the thermally expanded refractory resin composition of the present embodiment can be used after being formed into a putty shape, a sheet shape, or a paste shape. Moreover, you may use it in the state supported by the other base material.

  As described above, the thermal expansion fire-resistant resin composition of the present embodiment forms an expanded heat insulating layer during heating and further exhibits its remarkable fire resistance performance by maintaining its shape. It can be used. Moreover, it can be molded by ordinary equipment, for example, it can be molded into a sheet shape and can be suitably used for coating a building, etc. When it is liquefied, it can be applied in the same manner as a normal paint. When packed in an elastomer pack, it is possible to fill it with the contents that match the various shapes of the building by hand.

  The present invention will be described more specifically based on examples, but the present invention is not limited to this.

(Raw materials used)
The following raw materials were used.
-Epoxy resin (A):
Liquid epoxy resin 1 (Bisphenol F type, trade name: EP-4901, manufactured by ADEKA)
Liquid epoxy resin 2 (phenol novolac type, trade name: phenol novolac type epoxy resin, multifunctional type 152, manufactured by Mitsubishi Chemical Corporation)
Solid epoxy resin (bisphenol A type, trade name: EPICLON 7050, manufactured by DIC Corporation)
-Thermally expandable graphite (B):
Thermally expandable graphite (expansion start temperature: 200 ° C., trade name: SS-3, manufactured by Air Water Chemical)
Inorganic filler (C):
Surface-treated calcium carbonate (trade name: Shiraka Hana CCR, manufactured by Shiraishi Calcium)
Aluminum hydroxide (B-313, manufactured by Sakai Kogyo Co., Ltd.)
・ Flame retardant (D):
Ammonium polyphosphate (trade name: Exorit AP422, manufactured by Hoechst)
Triphenyl phosphate (TPP, manufactured by Daihachi Chemical Co., Ltd.)
Rubber component or thermoplastic elastomer component (E):
Rubber component Nitrile rubber (NBR) (trade name: Nipol DN1042, manufactured by Nippon Zeon)
Butyl rubber (IIR) (Brand name: BUTYL065, manufactured by JSR)
Chloroprene rubber (CR) (trade name: M-40, manufactured by Denka)
Styrene-butadiene rubber (SBR) (trade name: 1502, manufactured by JSR)
Ethylene-propylene rubber (EPDM) (trade name: EP-24, manufactured by JSR Corporation)
Thermoplastic elastomer Thermoplastic elastomer 1:
Modified silicone polymer (trade name: Exester ES-S3430, manufactured by AGC)
Thermoplastic elastomer 2:
Hydrogenated styrene thermoplastic elastomer (SEBS resin)
(Product name: Tuftec H1221, manufactured by Asahi Kasei Corporation)
・ Reactive curing agent:
Modified aliphatic polyamine-based curing agent (trade name: ADEKA HARDNER EH-6019, manufactured by ADEKA, which reacts with epoxy resin at room temperature)
・ Latent curing agent Imidazole-based latent curing agent (trade name: Curesol 2PHZ-PW, manufactured by Shikoku Kasei Co., Ltd.)
Plasticizer (non-reactive plasticizer that does not react with other components in the composition):
ED-512X (Daihachi Chemical Co., Ltd.)

(Manufacture of thermal expansion fire-resistant resin composition)
The raw materials having the composition shown in Table 1 were heated and kneaded using an open kneader (manufactured by Nippon Spindle Manufacturing Co., Ltd.) to obtain a mixed composition, and a sheet-like thermally expanded refractory resin composition sheet was obtained using a press. .
About the rubber component or thermoplastic elastomer component (E) used, the compatibility with an epoxy resin was evaluated by the following method.
Moreover, about the manufactured thermal expansion refractory resin composition, compatibility, self-adhesiveness, fire resistance, uncured property, and a softness | flexibility were evaluated by the following method.
In addition, about Examples 1-14 and Comparative Examples 1 and 2, all were measured in the state which left still at 23 degreeC after mixing for 1 week.
The results are shown in Table 1.

(Compatibility)
The rubber component or the thermoplastic elastomer component (E) is mixed with the epoxy resin (A) to form a mixture, and the rubber component or the rubber component or the thermoplastic elastomer component (E) is determined according to the oil retention test method defined in JIS A5751: 1995 “Oil building caulking material for building”. After holding the thermoplastic elastomer component (E) at 70 ° C. for 24 hours, the penetration width to a filter paper having a diameter of 11 cm corresponding to two types defined in JIS P3801: 1995 “filter paper (for chemical analysis)” is 10 mm or less, It was evaluated whether or not the penetration number was 3 or less. As a result, when the permeation width to the filter paper was 10 mm or less and the permeation number was 3 or less, it was determined as “compatible” (◯). On the other hand, when the permeation width to the filter paper exceeds 10 mm or the permeation number exceeds 3, it was determined as “no compatibility” (×).
In addition, when the composition was evaluated in the same manner as described above, the same result as that of the blend of the component (E) and the epoxy resin (A) was obtained.

(Self-adhesive)
Two sheets of 50 mm width × 100 mm length × 5 mm thickness were formed as test pieces using the obtained composition. The 50 mm × 100 mm area of each sheet was laminated and allowed to stand at room temperature for about 20 minutes, and the remaining 50 mm × 100 mm area was gripped with a tensile tester so that it could be peeled off (JIS K6848). , JIS K6854, or JIS Z0237). And the area | region which was not bonded together was grabbed using the tensile tester, and the peeling strength in the bonding interface of a 180 degree direction was measured with the tension speed of 50 mm +/- 5mm / min. As a result, the case where the base material fracture occurred outside the interface was evaluated as self-adhesive, and the case where the base material failure did not occur was evaluated as not self-adhesive.
As a tensile tester, Minebea Technograph TGE series, Shimadzu Corporation Autograph AG-Plus, etc. can be used, but Minebea Technograph TGE series was used in this example.
In addition, for the test piece that did not break the base material, the composition (50 mm width × 100 mm length × 1 mm thickness) was attached to the mounting panel in accordance with JIS Z0237: 2009 “13 holding power”, A test plate made of SUS (25 mm width × 150 mm length × 2 mm thickness) was bonded so that an area (one area) of 25 mm width × 100 mm length of the composition was covered, and the composition was used in an environment of 30 ° C. Self-adhesive when there is no deviation between the test plate and the composition after 1 hour when the load of 200 g is lowered at the end of the test plate that is not bonded to the test plate. (○), the case where there was no drop, but there was a shift, the self-adhesiveness was slightly but insufficient (Δ), and the case where there was a drop was evaluated as no self-adhesion (×).

(Fire resistance)
As an experimental ashtray, a circular ashtray having a heat-resistant temperature of 1000 ° C. (trade name: 12 ml of ashtray for ash measurement, product number: 2-8996-07, model number 204/4, manufactured by ASONE) was used. Specific specifications of the experimental ashtray are as follows: chemical composition: SiO ₂ /63%, Al ₂ O ₃ /30%, specific gravity: 2.4 g / cm ³ , capacity: 12 mL, size: φ47 mm (inner diameter) × 13 mm ( Height).
As a metal spoon, a stainless steel spoon (trade name: spoon (stainless steel) 180 mm (without spatula), product number: 6-522-04, manufactured by ASONE) was used. Specific specifications of the metal spoon were: material: stainless steel (SUS410), total length: 180 mm, type: scissors.
Using the obtained composition, a sheet of 5 mm width × 5 mm length × 3 mm thickness was formed as a test piece. This test piece is placed in a laboratory ashtray, placed in a furnace of a muffle furnace (Advantech Toyo FUM series) that can be heated up to 1000 ° C., heated up to 800 ° C. and kept for 20 minutes, and then in the furnace It was taken out from. After sufficiently cooling (room temperature), the metal spoon is allowed to fall freely from the position 1 cm above (1 cm height) to the periphery of the experimental ashtray, thereby scooping the metal spoon (protruding portion) I hit the experimental ashtray. By repeating this three times, hitting the experimental ashtray three times, if it strikes once and then crumbles, it is not fireproof (×), if it crumbles twice, it is fireproof (○), and even if tapped three times, it does not collapse The case was evaluated as having fire resistance (火).

(Uncured)
Hardness meter (product name: Asker rubber hardness meter A type, manufactured by Kobunshi Keiki Co., Ltd.) in accordance with JIS K6253-3: 2012 “Vulcanized rubber and thermoplastic rubber-Determination of hardness-Part 3: Durometer hardness” ) Was used.
Using the obtained composition, a 100 mm × 100 mm × 10 mm sheet was prepared as a test piece. The test piece was prepared such that a horizontal smooth surface having a size capable of being in close contact with the pressing surface of the hardness meter was secured.
When it was confirmed whether the measurement result had an influence on the hardness of the table on which the test piece of the hardness tester was placed, it was not affected.
The test piece was allowed to stand on the sample table of the hardness meter under an environment of 23 ° C., and the pressing surface of the hardness meter was pressed against the test piece simultaneously with the start of measurement by the stopwatch.
The numerical value (hardness) after 1 second and 5 seconds after the start was measured, and the ratio of the obtained numerical values was calculated using the following formula to calculate the hardness ratio as the degree of change (%). . When the degree of change was 20% or more, it was regarded as uncured (with uncured property). Moreover, when the degree of change exceeded 20% in 20% or more, it was considered as very uncured (very uncured). That is, when the degree of change was 20% or more and 25% or less, it was regarded as uncured (◯), and when it exceeded 25%, it was regarded as very uncured (硬化). On the other hand, the case where the degree of change was less than 20% was regarded as curing (no uncured property, x).
Degree of change (%) = {(number after 1 second) − (number after 5 seconds)} / (number after 1 second) × 100

(Flexibility)
The obtained composition was formed into the following shapes (1) and (2) to prepare a sample.
(1) 50 mm x 100 mm x 5 mm
(2) 50mm x 200mm x 5mm
Samples (1) and (2) were visually confirmed by the following methods (a) and (b) in a state where they were allowed to stand at 23 ° C. ± 2 ° C.
(A) (1) was wound around a pipe having a nominal diameter of 10A (outer diameter φ13), and it was confirmed that there were no cracks or cracks.
(B) (2) was wrapped around a pipe having a nominal diameter of 42A (outer diameter φ48), and it was confirmed that there were no cracks or cracks.
If neither cracks nor cracks occur in both (a) and (b), it is determined that the flexibility is very good (（), and cracks and cracks accompanying material destruction do not occur, but a small amount When a hair crack is entered, it was determined that the flexibility was good (◯), and if a crack or crack occurred, it was determined that there was no flexibility (×).

As a result, it was found that Examples 1 to 14 can achieve both a shape retention property (fire resistance) and a flexibility (workability) during combustion at a higher level than Comparative Examples 1 and 2.
It has been found that the liquid epoxy resin can improve the workability (flexibility) and improve the fire resistance more than the solid epoxy resin (Examples 1, 6 and 7). When there is too much solid epoxy resin, the flexibility tends to decrease. In Example 7, a plasticizer was added to improve the flexibility, so that this plasticizer caused the plasticizer to be more than in Examples 1 and 6. It is inferred that the degree of improvement in fire resistance has been reduced.
In addition, it was found that when the rubber component or the thermoplastic elastomer component is contained, the fire resistance can be improved as compared with the case where these components are not contained (Examples 1, 4, 5, and 13). Moreover, when containing a latent hardener, it turned out that fire resistance can be improved rather than the case where these are not contained (Examples 2-4).
Of the rubber components, it has been found that when nitrile rubber is contained, the fire resistance can be improved as compared with the case where other rubber is contained (Examples 1, 8, and 9).

Claims (2)

Epoxy resin (A),
Thermally expandable graphite (B);
An inorganic filler (C);
Containing a flame retardant (D),
The said epoxy resin (A) is a non-hardened thermal expansion refractory resin composition.   The thermal expansion fire-resistant resin composition of Claim 1 whose said flame retardant (D) is an inorganic phosphorus compound.