JP3133683B2 - Expandable resin composition for fire protection - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an intumescent resin composition for fire protection, and more particularly, it can be used in the form of a sheet or putty. The present invention relates to an expandable resin composition for fire prevention which is useful as a plugging material for a through portion of a fire retardant.

[0002]

2. Description of the Related Art In buildings such as factories and office buildings, through holes are formed in fireproof sections such as walls and floors that separate each other's living space, and polyvinyl chloride pipes and polyethylene pipes are formed in the through holes. Such a flammable resin pipe is inserted. In addition, air conditioning equipment piping and various electric cables are also inserted. However, when a fire occurs in a certain living space, the resin pipe, the foamed heat insulating material of the piping of the air conditioner, the coating of the electric cable and the like are burned or melted by the heat and the flame, and disappear. The hole becomes a flame path, and the fire spreads from here to the next room.

Conventionally, a so-called non-combustible material, such as a slate pipe, in which the outside of a resin pipe or the like is covered with a so-called fire-resistant double pipe is inserted into the through-hole, and the gap between the fire-resistant double pipe and the through-hole is mortar-filled. Fire-blocking methods are used to block with rock wool. However, this fire-resistant double pipe is quite heavy and has poor workability during transportation and construction. Also, once a fire occurs,
The inner pipe, such as a resin pipe, becomes steamed and generates harmful gas, and the harmful gas and the like may flow into the adjacent room due to the fact that it is impossible to completely close the through hole.

[0004] For these reasons, recently, the outside of a resin pipe or a pipe of an air conditioner is covered with a heat-resistant inflatable composition which expands and expands in volume when heated, and is coated with a fireproof compartment. In some cases, a structure that is inserted through a through hole in the body may be employed. In the case of this structure, when a fire occurs in a certain living space and the flame heat reaches the penetration part of the fire protection compartment, the expandable composition is heated and expands, and at that time, between the inflatable composition and the wall surface of the through hole. The generated pressure crushes the softened resin pipe or the foamed heat insulating material of the air conditioner pipe to block the entire through hole, thereby preventing the spread of fire.

[0005] As a heat-resistant expandable composition having such a function, a base resin such as polyvinyl chloride, chlorinated polyethylene, a copolymer of ethylene and ethyl acrylate, and a heat-expandable graphite have been used. , An ammonium polyphosphate, an inorganic swelling agent such as vermiculite, and an organic swelling agent such as an acid amide compound represented by azodicarbonamide are provided.

[0006]

However, although the above-mentioned expandable compositions provided so far expand under the influence of flame heat, the obtained expandable layer generally loses its shape as time elapses. It may wake up and collapse from the through hole in the fire protection compartment. Such a tendency is more remarkable when the expandable composition is putty-like.

Since the occurrence of such a situation is extremely inconvenient for preventing fire spread, it is necessary to use a large amount of the intumescent composition in advance at the time of construction so as to compensate for the amount of collapse of the intumescent layer. . However, such countermeasures not only increase the cost at the time of construction, but even if such countermeasures are taken, the collapse phenomenon of the expansive layer still continues to progress. It is difficult to secure the closed state for a long time.

[0008] Therefore, the expansible composition has a property that when it receives the flame heat, it expands at a large expansion ratio and can completely close the through-hole of the fire protection compartment with the expanded layer, and also has the flame heat. Even if the expansion layer is continuously received, it is required that the formed expanded layer does not lose its shape and maintain its shape for a long period of time. In addition, in the case of this expandable composition, when the period from when it is manufactured at the factory to when it is provided for construction is long, when the storage process deteriorates and, for example, the expansion ratio decreases, the expansion of the expandable composition occurs. The flammable composition will not exhibit the fire prevention performance originally assumed. In addition, if the expandable composition hardens during the storage process, the workability in actual use will deteriorate.

[0009] Therefore, the expandable composition to be practically used is not deteriorated even during a long-term storage process, that is, if the composition is excellent in preservability, it is easy to stock and is suitable. An object of the present invention is to provide an intumescent resin composition for fire protection having excellent shape retention. It is a further object of the present invention to provide a novel fire-retardant expandable resin composition having a good balance of expandability, shape retention and storage stability.

[0010]

In order to achieve the above-mentioned object, in the present invention, an inorganic expanding agent and / or an organic expanding agent and a shape-preventing resin are simultaneously mixed with a base resin. There is provided an intumescent resin composition for fire protection characterized by comprising:

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The base resin in the resin composition of the present invention is not particularly limited. However, when this resin composition is actually used, it is inserted into the through hole of the fire protection compartment and therethrough. Considering that the use form of filling the gaps between various pipes and cables as putty or covering the outer circumference of various pipes and cables in a sheet shape is adopted, the base resin is flexible. It is preferable to use one provided with

In this case, as the base resin, either a solid polymer or a liquid polymer can be used, or both can be used as a mixture. Also,
It is also possible to use a material such as urethane rubber, which is changed into a solid by reacting a raw material supplied in a liquid state. Suitable solid polymers include flexible rubbers and thermoplastic elastomers.

By using rubber or a thermoplastic elastomer as the base resin, workability during construction is improved.
Further, the rubber does not melt and become liquid even when heated, and the resin composition using the rubber does not flow away from the construction site when a fire occurs, so that the through hole can be completely closed reliably. Specifically, natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, epichlorohydrin rubber, Solid rubbers such as silicone rubber and fluorine rubber; and thermoplastic elastomers such as styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and PVC-based thermoplastic elastomers.

Among them, heat resistance, weather resistance and ozone resistance are good, and even after storage for a long time, proper flexibility is maintained and workability is not deteriorated. Ethylene-propylene rubber and butyl rubber, which hardly cause deterioration even when used as a putty or a sheet, are suitable base resins. Any ethylene-propylene rubber may be used as long as it is conventionally known. For example, an ethylene-propylene copolymer (EPM) synthesized from only ethylene and propylene and having no double bond in the molecule,
No. 3 which forms a side chain in a copolymer of ethylene and propylene
Examples thereof include an ethylene-propylene terpolymer (EPDM) into which a group having a double bond is introduced as a component, and a blend of both.

[0015] The butyl rubber is not particularly limited, and a conventionally known butyl rubber can be used. Although the above-mentioned solid polymer alone functions sufficiently as a base resin, when a liquid polymer is further blended with these solid polymers to form a base resin, the moldability of the obtained resin composition becomes very good. That is, when the obtained resin composition is used as a sheet, the dimensional stability at the time of sheet molding is improved, and the workability is extremely good. Has the appropriate flexibility, making the construction work very easy.

In this case, when the liquid polymer is formed into a sheet with the resin composition by adjusting the strength of rubber elasticity of the base resin, the molded thickness of the sheet is increased by the rubber elasticity of the base resin, and the dimensions are stable. It suppresses that the property falls. However, when the liquid polymer has an alcoholic OH group, when an acid amide-based compound described later is used as an organic expanding agent, the resin composition hardens during the storage process as described later. It is preferable to use a polymer having no OH group as the liquid polymer, since the storage property of the polymer decreases. Specifically, any one of polybutadiene, chloroprene, polybutene, and polyisoprene
Species or two or more species can be mentioned as preferred examples.

At this time, if the amount of the liquid polymer to the solid polymer is too small, the dimensional stability of the molded sheet made of the resin composition of the present invention is deteriorated, and the molded sheet becomes too hard. Makes filling work difficult, especially in winter.
On the other hand, if the amount of the liquid polymer is too large, the molded sheet becomes too sticky and difficult to perform, and the liquid polymer bleeds out during long-term storage, causing a decrease in the adhesiveness to a resin pipe or the like.

When a solid polymer and a liquid polymer are blended to form a base resin, the blending ratio of the two is appropriately set in consideration of the occurrence of the problems described above. The liquid polymer can be used alone as a base resin. For example, one or more of polybutadiene, chloroprene, polybutene and polyisoprene can be used alone as a base resin. In that case, it should be noted that the softness is adjusted by adding an appropriate amount of a filler such as clay, talc, calcium carbonate, and measures are taken to ensure the shape after construction. .

Further, by blending a plasticizer with the above-mentioned solid polymer, flexibility may be imparted to the obtained resin composition, and for example, the moldability during sheet molding may be enhanced. In particular, when the above-mentioned solid rubber is used as the solid polymer, the compounding of a plasticizer is preferable. In that case, if the blending amount of the plasticizer is too small, the flexibility of the obtained resin composition is deteriorated, and the moldability is reduced, and at the time of molding, the whole is too hard even if, for example, a large amount of the liquid polymer is blended. Causes a decrease in workability. On the other hand, if the amount is too large, the plasticizer oozes out during storage for a long period of time and the adhesiveness to resin pipes and the like decreases, and the ooze out of the plasticizer migrates to the resin pipe or cable coating layer side. Adversely affect the resin pipe.

From the above, when a plasticizer is blended in the base resin, it should be noted that the blending amount of the plasticizer is adjusted in consideration of the above-mentioned problems. Examples of the plasticizer having such a function include, for example,
Phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl octyl phthalate and dioctyl phthalate; adipic acid derivatives such as dioctyl adipate and diisooctyl adipate; di-n-butyl malate and diethyl Malate, di- (2-
Maleic acid derivatives such as ethylhexyl) malate;
In addition, succinoic acid derivatives can be mentioned.

When urethane rubber is selected as the base resin, it is difficult to use a crosslinked resin as a putty. However, it is sufficiently possible to make a sheet and wind it around a pipe or the like. In this case, any urethane rubber may be used as long as it is conventionally known. Next, the swelling agent blended in the base resin may be any of an inorganic type and an organic type,
Moreover, you may mix and use both together.

Generally, as a material for expanding the resin composition, a foaming agent which generates a decomposed gas by being thermally decomposed when heated and expands the resin composition by the pressure of the decomposed gas is known. In the present invention, the expanding agent is referred to as the swelling agent including the above-mentioned blowing agent. These expanding agents expand the resin composition by being foamed when heated, thereby converting the resin composition into an expanding layer, and coating the resin pipes and cables inserted into the through holes by the pressure generated at that time. At the same time as squeezing the foam and the foamed heat insulating material of the pipes, it functions to close the through holes with the expansion layer.

Preferred examples of the inorganic expansive agent include expansive graphite, borax, vermiculite, and pearlite. Each of these may be used alone, or two or more of them may be appropriately mixed and used. In the above-mentioned inorganic swelling agents, the decomposition temperatures of borax, expandable graphite, vermiculite, and pearlite are 100 to 15 respectively.
0 ° C, about 300 ° C, about 500 ° C, and about 500 ° C.

Therefore, when an inorganic expanding agent is used, borax or thermally expanded graphite which starts to expand at a relatively low temperature is contained as an essential component, and further, burble or pearlite which expands at a relatively high temperature. In the event of a fire, in the event of a fire, the resin composition continues to expand in a relatively early stage from the low-temperature stage to the high-temperature stage, and the expansion layer continues to be formed. It is possible and suitable.

Of these, crushed raw stone that has not been fired is used as the vermiculite. This vermiculite
When heated rapidly, it expands as if the accordion of the instrument were open. However, since the expansion occurs partially, the resin composition has a somewhat insufficient performance in that the entire resin composition is uniformly expanded. Borax has a relatively low expansion start temperature and a large expansion ratio. However, after expansion, 300 ° C
It has the property of melting when heated to the above temperature, and its use alone may not provide sufficient fire resistance.

On the other hand, the expandable graphite is formed by depositing a thermally decomposable substance between the layers of the hexagonal crystal in which the layers of the network plane of the six-membered ring structure extending two-dimensionally and the layers are stacked in the c-axis direction. Intercalation compounds that have been inserted, such as fuming sulfuric acid, sulfuric acid and concentrated nitric acid, various nitrates, perchloric acid, various perchlorates, chromic acids, various chromates, dichromates, etc. It is manufactured by immersing graphite in a neutral solution, washing with water and drying.

When the expandable graphite is rapidly heated, the compounds inserted between the layers and the compounds inserted into the crystal grain boundaries are thermally decomposed, and the pressure between the layers is increased by the pressure of the decomposition gas generated at that time. It is spread and expanded. There is a correlation between the particle size of the expandable graphite and the expansion ratio. In general, the larger the particle size, the larger the expansion ratio. In the present invention, those having a particle size of 300 μm or more are particularly preferably used.

The expandable graphite has a helical structure when viewed macroscopically, but has a honeycomb structure when viewed microscopically. It is extremely large compared to borax, and has a feature that the expansion force does not decrease even when the temperature is 300 ° C. or more. From such a fact, in the resin composition of the present invention,
It is preferable that this expandable graphite is contained as an essential component as an inorganic expander.

As the organic expanding agent, azodicarbonamide, azodiaminobenzene, N, N'-dinitroso-
Preferred examples include N, N'-dimethylterephthalamide, benzenesulfonylhydrazide, p, p'-oxybisbenzenesulfonylhydrazide. Each of these may be used alone, or 2
Mixtures of more than one species may be used.

Each of these organic expanding agents has a decomposition temperature of about 100 to 200 ° C., exhibits a high expansion ratio, and has a high decomposition rate. Can be inflated. Therefore, the resin composition is a resin pipe or cable coating layer,
The power of crushing foam insulation material in a pipe in a short time in a concentrated manner is further increased so that the penetration portion is efficiently closed.

The resin composition of the present invention is characterized in that, in addition to the above-mentioned components, a shape-preventing resin is simultaneously compounded and dispersed. Here, the shape-preventing resin referred to in the present invention is a resin that prevents a time-dependent collapse phenomenon of an expanded layer formed by expanding the resin composition when subjected to flame heat, that is, the shape of the expanded layer. It refers to a resin that works to enhance the retention.

The shape-preventing resin functions as follows. That is, when the resin composition is heated to a temperature equal to or higher than the glass transition temperature of the shape-preventing resin dispersed therein, the shape-preventing resin is softened or partially melted, and finally carbonized. In the process, the resin composition is converted into the expanded layer, but the softened or partially melted resin for preventing shape loss is carbonized so as to cover the skeleton portion of the formed expanded layer. Has the effect of reinforcing the strength of the skeleton portion of the inflatable layer, thereby increasing the mechanical strength of the entire inflatable layer and preventing its collapse. Such a function is more effectively exhibited as the shape-preventing resin is more uniformly dispersed in the resin composition.

The shape-preventing resin may be used by dispersing the granular resin as it is in the composition, or by dissolving the pellet-shaped resin in an appropriate solvent and dispersing it. In any case, it is important to uniformly disperse these resins in the resin composition to prevent the above-mentioned expansion layer from being deformed. In addition, the application of the manufactured resin composition is often performed manually in a room, and the workability may change due to evaporation of the solvent during storage, so that the resin is not dispersed in the solvent. It is preferable to use a type, and it is preferable to use a granular type as it is.

The granular resin is easily dispersed uniformly in the base resin, the workability of the obtained resin composition is good, and it is also effective in preventing the expansion layer from deforming. The shape-preventing resin is appropriately selected in relation to a swelling agent that is simultaneously added to the base resin. In the present invention, when the above-mentioned expandable graphite is used as an expanding agent, polycarbonate resin (PC), polyphenylene sulfide resin (PP
S), polyphenylene ether resin (PPE), polyether ketone resin (PEK), polyether ether ketone resin (PEEK), polyether sulfone resin (P
ES), polysulfone resin (PSF), polyamide resin (PA), polyarylate resin (PAR), and polyetherimide resin (PEI) can be mentioned as preferred examples. Each of these resins may be used alone, or two or more of them may be used in an appropriate combination.

[0035] These resins are both when heated are each melted at a predetermined temperature to coat the skeleton portion of the expandable layer, solidifying the expansion layer, allowed to ensure their shape retaining property. In that case, it is preferable that the melting start temperature of the resin to be used is equal to or close to the decomposition expansion start temperature of the expanding agent blended in the resin composition. This is because, in the process of forming the inflatable layer, the skeleton portion of the inflatable layer that is being formed is almost simultaneously covered with the melting prevention resin that has been melted and solidified.

Among the above resins for preventing shape loss, those having a molecular structure in which another element is bonded to an aromatic group through an ether bond or a thioether bond are more excellent in the ability of the expanded layer to prevent shape loss. So useful. In particular,
PC, PPS, PPE, PEK, PEEK, PES, P
SF, PAR, PEI and the like can be mentioned, and among them, PC, PPS and PPE are preferable because they have remarkably excellent shape-preventing ability.

It is not clear why PC, PPS, PPE and the like exhibit excellent shape-preventing ability, but when the resin is melted by flame heat to cover the skeletal portion of the expanded layer, and when the temperature further rises, these resins become insoluble. It is presumed that in the case of a resin, a rearrangement reaction occurs and the resin is changed to a phenolic resin, which tends to cause carbonization. In particular, when expandable graphite is used as the expandable agent, the expansion start temperature of the expandable graphite is about 300 ° C. The above-mentioned PC, PPS, PPE and the like also differ depending on the molecular structure. 20
This is considered to be because the temperature is about 0 to 300 ° C., and the action of solidifying the expansion layer at the same time as its formation is effectively exhibited.

In the case of PC, PPS, and PPE, they can be uniformly dispersed without dissolving in suitable base resins such as butyl rubber, ethylene propylene rubber, butadiene rubber, polybutene, and polybutadiene.
The reinforcing effect of the expanding layer is effectively exhibited, and an excellent shape-preventing effect is exhibited. PC is the following formula:

[0039]

Embedded image

(R represents an aliphatic group or an aromatic group. N
Is an integer. ), And its melting point changes depending on the type of R and the n value. If a material having an excessively high melting point is used, it may not be melted even after the formation of the intumescent layer, so that the above-mentioned shape retention performance with respect to the intumescent layer is reduced. From this point, when expandable graphite is used as the expanding agent, PC is preferably a bisphenol A type having an aromatic group.

Specifically, PC having a number average molecular weight of about 10,000 to 30,000 is preferable as PC. PC having a molecular weight in this range has a melting point of 200 to 300 ° C.
And the viscosity after melting is small, so that the expansion force of the expandable graphite is not hindered in the process of expanding the expandable graphite and converting the resin composition into an expandable layer. This is preferable because the expansion ratio of the layer increases.

The PC is preferably used as it is in the form of particles obtained by pulverizing a block of the synthesized PC. The particle size at this time is an average particle size of 5 to 1000 μm, particularly 10 to 10 μm.
Preferably it is 500 μm. At this time, good uniform dispersion in the base resin becomes possible, and the workability of the resin composition is improved, which is preferable.
The target resin composition may be dispersed in an aromatic hydrocarbon such as benzene or toluene, and the resulting dispersion is kneaded with a base resin and expandable graphite.

Further, PPS and PPE are respectively represented by the following formulas:

[0044]

Embedded image

The melting point changes according to the n value. These are also used in actual use in the same usage form as the case of the above-mentioned PC, and effectively function as a resin for preventing shape collapse in the resin composition of the present invention .

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

On the other hand, the aforementioned PC, PPS, PP
E, PEK, PEEK, PES, PSF, PA, PA
R and PEI do not have alcoholic OH groups, so that the above-mentioned decrease in softness does not occur when a phenol resin is used. In addition, the expandability is good, and the property of preventing the shape of the formed expandable layer from being practically sufficient,
The fire resistance is also good, and the resin composition is suitable in that it can be used both as a putty and as a sheet.

In the resin composition of the present invention, the amount of the base resin is preferably 10 to 50% by weight based on the total amount of the resin composition. If the amount is less than 10% by weight, there is a difficulty in maintaining the shape of the obtained resin composition even when the obtained resin composition is used in a putty form or in a sheet form. . In other words, when used in a putty shape, it is uneven and poor in filling properties, and when used in a sheet shape, it can be wrapped around piping and only a certain degree of flexibility is obtained. It is.

When the amount is more than 50% by weight, the obtained resin composition has too high elasticity, so that it becomes difficult to form a sheet. The compounding amount of the inorganic swelling agent and / or the organic swelling agent is 3 to 3 in total.
It is preferably set to 0% by weight. When the amount is less than 3% by weight in total, the resin composition does not expand sufficiently, which tends to hinder the operation of closing the through-hole. If the amount is more than 30% by weight, the expanding agent falls off at the time of forming the sheet, which makes it difficult to form the sheet. In addition, the expansion ratio of the resin composition becomes too large, and the resin composition may lose its shape. Absent.

Further, expandable graphite is used as a swelling agent, and PC, PPS, PPE, PEK,
In the resin composition manufactured using PEEK, PES, PSF, PA, PAR, PEI, and phenolic resin, the compounding amount of the shape-preventing resin is 15% of the entire resin composition.
It is preferably set to 〜60% by weight. If the compounding amount is less than 15% by weight, the shape-retaining property of the expanding layer formed at the time of flame heat cannot be sufficiently ensured, the effect of preventing shape collapse is reduced, and the compounding amount is more than 60% by weight. Then, expansion of the resin composition is inhibited.

In the resin composition of the present invention, in addition to the above-mentioned components, an appropriate amount of an antioxidant or a fiber chip may be added, or a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide. May be added to impart flame retardancy. In addition, fillers such as clay, talc and calcium carbonate can be converted to improve workability and shape retention.

[0059]

【Example】

Examples 1 to 32 and Comparative Examples 1 to 7 The following materials were prepared. Base resin: EPDM: EP-96 (trade name, ethylene-propylene-terpolymer manufactured by Nippon Synthetic Rubber Co., Ltd.) Butyl rubber: 065 (trade name, Nippon Synthetic Rubber Co., Ltd.)
Made).

Butadiene rubber: BR01 (trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.). The above three are solid rubbers. Polybutene: HV-15 (trade name, manufactured by Nippon Petrochemical Industry Co., Ltd.). Hydroxyl-terminated polybutadiene: Poly bd R-45HT (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.).

Polybutadiene: B-2000 (trade name,
Japan Petrochemical Industry Co., Ltd.). The above three are liquid polymers. Castor oil: URICY-403 (trade name, manufactured by Ito Oil Co., Ltd.). Polymethylene polyphenyl isocyanate: Millionate MR200 (trade name, manufactured by Nippon Polyurethane Co., Ltd.).

Plasticizer: Dioctyl phthalate: manufactured by Kyowa Hakko Co., Ltd. Swelling agent: Borax: Neo Blacks G (brand name, United States &
Chemicals).

Expandable graphite: SG-01 (trade name, manufactured by Nippon Kasei Kogyo Co., Ltd.). Hiruishi: Vermiculite No. 1 (trade name, manufactured by Showa Vermiculite Co., Ltd.). Pearlite: Pearlite polished stone A (trade name, manufactured by Mitsui Kinzoku Perlite Co., Ltd.).

Resin for preventing shape loss: Phenol resin: Resol type phenol resin having a number average molecular weight of about 100,000 is pulverized to an average particle diameter of 50 μm. Polycarbonate resin (PC): Number average molecular weight is about 2.5
10,000 polycarbonate resins are crushed and the average particle size is 30 μm
What you did.

Polyphenylene ether resin (PPE):
Ubiace YPX-100L (trade name, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) is pulverized to an average particle size of 3
Thickened to 0 μm. Polyphenylene sulfide resin (PPS): T-1
(Trade name, manufactured by Topren Co., Ltd.)
Thickened to 0 μm.

Polyetherketone resin (PEK): “V
ICTOREX ”PEK (trade name, ICI
(Made by Japan Co., Ltd.) into an average particle size of 30 μm. Polyetheretherketone resin (PEEK): "VI
CTOREX ”PEEK (trade name, ICI
(Made by Japan Co., Ltd.) into an average particle size of 30 μm.

Polyether sulfone resin (PES):
"VICTOREX" PES (trade name, manufactured by ICI Japan KK) pulverized to an average particle size of 30 µm Polysulfone resin (PSF): UDELP-1700
(Trade name, manufactured by Amoco Japan Limited) having a mean particle size of 30 μm.

Polyamide resin (PA): Leona 1300
S (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) having a mean particle size of 30 μm. Polyarylate resin (PAR): U polymer U-10
No. 0 (trade name, manufactured by Unitika Ltd.) is crushed to have an average particle size of 30 μm. Polyetherimide resin (PEI): Ultem 1000
(Trade name, manufactured by Nippon GE Plastics Co., Ltd.) crushed to an average particle size of 30 μm.

Epoxy resin: An epoxy resin obtained by mixing 50 parts by weight of an amine-based curing agent Evomate B-200 with 100 parts by weight of Epicoat 828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) and curing at 100 ° C. for 30 minutes. Crushed to an average particle size of 30 μm. Polyvinyl chloride resin (PVC): Ryulon TH-10
00 (trade name, manufactured by Tosoh Corporation) having an average particle size of 30 μm.

Polyethylene resin (PE): Admer NE
050 (trade name, manufactured by Mitsui Petrochemical Co., Ltd.) having a mean particle size of 30 μm. Each of the above components shown in Tables 1 to 20 was kneaded at the indicated ratio in a kneader having a capacity of 75 liters, and the moldability, workability, uniformity, expansion ratio, shape collapse, dropping properties, and combustion characteristics of each kneaded product were obtained. And the softness were evaluated according to the following specifications.

Formability: The kneaded material was formed into a sheet having a thickness of about 5 mm with a roll, and the obtained sheet was cut with a stainless steel blade.
The ones that could be easily cut were marked with 、, those that were too sticky and could not be cut because they adhered to stainless steel blades, and those that could not be cut cleanly because they collapsed during cutting, and that the dimensions expanded due to expansion after molding. Those that were stable were marked with ▽.

Putty workability: ○: workable in both summer and winter; ○: hard and difficult to work in winter; Δ: soft and difficult to work in summer . This evaluation was performed only for putty-like ones. Expandability: As shown in FIG. 1, a copper tube is erected on an iron plate 1,
The copper tube 2 was fixed with silicone rubber 3, and a predetermined volume of the kneaded material 4 was put in the copper tube and heated at a temperature of 300 ° C. for 30 minutes to expand. The volume after expansion was divided by the volume before expansion to calculate the expansion ratio (times).

The putty was 30 mm long, 30 mm wide, and 5 mm thick.
It was cut into a size of mm, heated at a temperature of 300 ° C. for 30 minutes to expand, and the state after expansion was examined. ×: when the expanded material collapsed and cracked, ○ when it was not collapsed by visual inspection, ◎ when it did not collapse even if it was touched by hand
And Dropping property: First, the following simple refractory furnace was assembled. As shown in FIGS. 2 and 3, the height is 210 mm and the groove width is 200 m.
Two 25 mm thick fire-resistant plates 6 each having a recess 6a were fitted into a concrete trough 5 having a length of 300 mm and a thickness of 30 mm to form a space having an upper opening in the trough 5.

On the other hand, a through-hole having a diameter of 38 mm was formed in the center of the refractory plate 6A having a thickness of 25 mm, and a copper tube 7 having an outer diameter of 38 mm and a length of 50 mm was inserted through the through-hole as shown in FIG. Further, a polyvinyl chloride pipe 8 having a diameter of 24.5 mm and a length of 150 mm was inserted into the center of the copper pipe 7, and the kneaded material 4 was filled between the copper pipe 7 and the pipe 8.

Then, the refractory plate 6A was arranged at the upper opening of the trough 5 and a thermocouple 9 was embedded in the kneaded material 4 to form a simple refractory furnace. Next, the burner 10 was placed in the recess 6a of the refractory plate 6, and a flame having a temperature of about 900 to 1000 ° C. was blown, and the kneaded material 4 and the pipe 8 were heated to expand the kneaded material 4.

After the expansion, the weight of the kneaded material dropped into the trough was measured. The case where no drop occurred was indicated by ◎, the case where the drop amount was 10% or less of the initially charged amount was indicated by ○, the case where the drop amount was 10 to 25% was indicated by Δ, and the case where the drop amount was 25% or more was indicated by ×. Combustion test (Evaluation 1): A through-hole having a diameter of 80 mm was formed in a vertical wall, and a cross-linked polyethylene tube having an outer diameter of 27 mm was covered with foamed polyethylene to form a tube having an outer diameter of 67 mm.
This was inserted. Then, the kneaded material was filled into the gap with 260 cm ³ , and the outside was held down with metal fittings, and the whole was fixed to the wall. In this state, the kneaded material was expanded by heating for 2 hours according to a temperature curve defined by JIS A1304. The time it took for the smoke to stop through the tube was measured.

◎: when the time until the smoke stopped was within 15 minutes, ○: when the time was within 15 to 30 minutes, 、: 30
Min. Or more, and x when the through-hole was not closed. Combustion test (Evaluation 2): A combustion test was performed using the same test apparatus as in the above-described combustion test (Evaluation 1). A steel ball having a mass of 1 kg was dropped onto the tube from a height of 2 m above, and the shape of the expanded layer was observed. The case where the shape deformation of the expansive layer did not occur was evaluated as ○, and the case where the shape deformation occurred was evaluated as ×.

This evaluation test was conducted in a state where the resin composition (kneaded material) was actually used as a putty (state of evaluation 1).
This is a test for evaluating whether even if a falling object hits a pipe or the like at the time of a fire, the impact at that time causes the expansion layer to fall off and cause a reduction in fire resistance performance. Combustion test (Evaluation 3): Only the kneaded material was filled into the through hole without inserting a pipe into the through hole of the vertical wall adopted in the combustion test (Evaluation 1), and the surface of the kneaded material was flush with the wall surface Then, the through-hole was closed. Next, the kneaded material was expanded by heating for 2 hours in the same manner as in the case of the combustion test (evaluation 1), and the state after 2 hours was observed.

When the crack did not enter and did not fall into the expansive layer, ◎ was given, when the crack entered but did not fall off, ○ was given, and when the crack entered and fell off, × was given. In the case of ×, the amount of remaining putty (% by weight)
Was calculated. According to this combustion test (Evaluation 3), a state similar to the case where a fire protection treatment is applied to a portion piped to a through hole having a large diameter appears, and therefore, when used in a through hole having a large diameter, Since it is possible to determine whether or not the kneaded material (putty) undergoes shape collapse, it is possible to evaluate the superiority of shape collapse prevention (shape retention) during actual use.

Softness: Measured according to the method specified in JIS A5752-1975 “Glass Putty for Metal Fittings”, paragraphs 5 and 4. Each kneaded material is 50mm long, 50mm wide and 5mm thick
, And the four sheets are stacked and left at a temperature of 23 ± 3 ° C. for 3 hours or more.
The needle for measurement in ° was inserted for 5 seconds at a total weight of falling of 150 g, the amount of insertion (mm) was measured, and this value was used as an initial value (in the table, expressed in units of 1/10 mm).

Further, the penetration amount after the four stacked samples were left in the air at 60 ° C. for 7 days was also measured. This test was performed only on putty. The above results are collectively shown in Tables 1 to 20.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

[Table 9]

[0091]

[Table 10]

[0092]

[Table 11]

[0093]

[Table 12]

[0094]

[Table 13]

[0095]

[Table 14]

[0096]

[Table 15]

[0097]

[Table 16]

[0098]

[Table 17]

[0099]

[Table 18]

[0100]

[Table 19]

[0101]

[Table 20]

The following is clear from the displayed results. (1) In the resin composition of the present invention, as apparent from Example 10, butyl rubber (solid polymer) alone can be used as a base resin.
As apparent from the above, liquid butadiene (liquid polymer) alone can be used as the base resin. Then, as is apparent from Examples 1 to 9 and Examples 13 to 32, solid polymers such as butyl rubber, EPDM, butadiene rubber, styrene-butadiene rubber, and polybutene were used.
A mixture obtained by kneading a liquid polymer such as polybutadiene, hydroxyl-terminated polybutadiene or the like can also be used as the base resin.

(2) As is apparent from Example 14, even if a urethane rubber is used as the base resin, the resin composition obtained can be used as a molded sheet, although the putty is not applicable. (3) As is clear from the comparison between Example 2 and Comparative Example 2,
When azodicarbonamide is used as a swelling agent, when the base resin contains a liquid polymer having an OH group (Comparative Example 2), the softness decreases with time, and there is a problem in storage stability. However, in the case of Example 2, the softness did not decrease, and good preservability was secured.

(4) Regardless of whether the organic and inorganic swelling agents are used in combination (Examples 1, 2, and 6), or the inorganic swelling agent is used alone (other examples). Each of the resin compositions expands sufficiently, and the obtained expanded layer does not collapse and is excellent in dropping property .

[0105]

( 5 ) PC or PP as a resin for preventing shape collapse
S, PPE, PEK, PEEK, PES, PSF, P
When A, PAR, and PEI are used, even when the inorganic expanding agent is used alone as the expanding agent (Examples 3, 4, 7 to 30), the inorganic expanding agent and the organic expanding agent are used together (Example) Even in the cases of (1) and (2), the expansion ratio is large, the shape does not collapse, the dropping property is excellent, the evaluation in the combustion test is good, and further, the softness is not reduced and the storage property is extremely excellent. That is, it is excellent in the balance between expandability, shape retention, and storage stability. In particular, PC, PPE, and PPS function as very excellent shape-prevention resins.

( 6 ) In the case of the resin composition of the example using expandable graphite as the expandable agent, as the expandability of the expandable graphite is large, as apparent from the combustion test (evaluation 1), The through hole is closed in a short time to stop the outflow of smoke. On the other hand, in the case of the resin composition not using the expandable graphite (Examples 15 to 19), it takes 1 to stop the outflow of the smoke.
It takes 5 to 30 minutes.

Even when such an expandable graphite having a strong expansion force is used, if the resin such as PC described above (Examples 1 to 4, 7 to 14, 20 to 32) is used as the resin for preventing shape collapse, As is clear from the combustion test (evaluation 2 and 3), shape collapse is hard to occur. Among these, PA is slightly inferior, but PC, PPE and PPS show very excellent results. However, expandable graphite is used, and epoxy resin, PVC, P
When E was used (Comparative Examples 1, 5 to 7), the shape was severely deformed.

( 7 ) The compounding amount of the shape-preventing resin is 15 to
The resin composition of 60% by weight does not lose its shape in the expanded layer and has excellent combustion characteristics. However, if the amount is 1
When the amount is less than 5% by weight (Comparative Example 3), the shape is remarkable and the dropping property is poor, and the closed state of the through hole cannot be sufficiently secured. When the blending amount is more than 60% by weight (Comparative Example 4), the shape does not collapse and the dropping property is good.
On the other hand, the formability and workability deteriorate, and it is difficult to actually use it.

The PC in Comparative Examples 3 and 4 was replaced with PP
S, PPE, PEK, PEEK, PES, PSF, P
A similar tendency was observed when A, PAR, or PEI was used.

[0111]

According to the first aspect of the present invention, when the resin composition is heated by contacting with flame heat, the inorganic expander and / or the organic expander foams and is entirely converted into an expandable layer. Then, the expansion force at that time crushes the resin pipe or the foamed heat insulating layer that has been softened by receiving heat, thereby closing the through hole of the fire protection compartment into which the resin pipe or the like is inserted. At this time,
Since the shape-prevention resin that has been blended is melted in the heating process and then heat-cured to exert a reinforcing effect on the skeletal portion of the expansion layer, the expansion layer does not collapse and keeps its shape, It does not fall from the through hole, and the closed state of the through hole is reliably maintained, effectively preventing fire from spreading.

[0112] The resin composition of claim 1 and, at the same time is excellent in long-term storage properties, expansion ratio can be more reliably achieve occlusion of the through-hole becomes large, the formed intumescent layer Fire resistance is excellent. That is, swelling,
Excellent balance between shape retention and storage. In particular,
The resin composition according to claim 2 has excellent expandability by using PC, PPE, and PPS as the shape-preventing resin with respect to expandable graphite, which is an expander, and has good shape expansion of the expandable layer. It demonstrates extremely good performance in that it does not wake up.

Since the resin composition of the third aspect uses rubber, thermoplastic elastomer or liquid polymer as the base resin, it can be used as a flexible sheet or putty as required. Since the resin for preventing shape collapse is appropriately dispersed in these base resins, the effect of preventing shape collapse is remarkably excellent.

As described above, the expandable resin composition for fire protection of the present invention has excellent moldability and workability, and can be used as a sheet or putty by using a combination of an expander and a resin for preventing shape loss. Yes, and does not decrease in softness even after long-term storage. And, when it comes into contact with the flame heat, it expands with a large expansion ratio, the formed expansion layer does not collapse and has excellent shape retention, and the through hole of the fire prevention compartment can be reliably closed to prevent fire spread. .

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining a method for measuring the expansion ratio of a resin composition.

FIG. 2 is a sectional view showing a simple refractory furnace.

FIG. 3 is a perspective view showing a simple refractory furnace.

FIG. 4 is a partial cross-sectional view showing a state in which a resin pipe is inserted into a through hole of a refractory plate and further filled with a resin composition.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Iron plate 2 Copper tube 3 Silicone rubber 4 Kneaded material (resin composition) 5 Trough 6, 6A Fireproof plate 6a Depression 7 Copper tube 8 Vinyl chloride pipe 9 Thermocouple 10 Burner

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masanori Owari 5-18-8 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside Furukawa Techno Material Co., Ltd. (72) Inventor Tadashi Naruse 5-1-1-8 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Stock Shares Inside the Furukawa Techno Material Co., Ltd. Inside the Saitama Plant Co., Ltd. (72) Inventor Hiroaki Tsumoda 306, Kamifomi, Miyoshi-cho, Iruma-gun, Saitama Towa Kogyo Co., Ltd. Saitama Plant (56) References Special Table 3-3-1654 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08J 9/06-9/10

Claims (3)

(57) [Claims] 1. An inorganic and / or organic swelling agent, a polycarbonate resin, a polypropylene
Nylene sulfide resin, polyphenylene ether tree
Fat, polyetherketone resin, polyetheretherke
Resin, polyether sulfone resin, polysulfone tree
Fat, polyamide resin, polyarylate resin, polyether
At least one form collapse selected from the group of ruimide resins
FIRE expandable resin composition and preventing resin is characterized by comprising blended. 2. An expandable graphite is used as the inorganic expander.
In addition, polycarbonate resin is used as the shape-preventing resin.
Fat, polyphenylene sulfide resin, polyphenylene
Using at least one selected from the group of ether resins
The intumescent resin composition for fire protection according to claim 1 comprising: 3. A butyl rubber, an ethylene resin or the like as the base resin.
Propylene rubber, butadiene rubber, polybutene,
Using at least one selected from the group of lipadiene,
Using expandable graphite as the expanding agent, for preventing the shape collapse
Polycarbonate resin, polyphenylene sal as resin
Select from the group of Fido resin and polyphenylene ether resin
2. The expansive tree according to claim 1, wherein said expansive tree comprises at least one of
Fat composition.