JP2014159541A - Thermally expandable fire-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermally expandable fire-resistant resin composition excellent in fire resistance, water resistance, and moldability.SOLUTION: The thermally expandable fire-resistant resin composition contains 100 pts.wt. of a resin component, 5-200 pts.wt. of thermally expandable graphite, 20-200 pts.wt. of a boron-containing compound, 10-70 pts.wt. of an antimony-containing compound, and 0.1-10 pts.wt. of a vulcanizing agent. The resin component contains at least one selected from the group consisting of EPDM, polybutene, and polybutadiene. A foaming agent can be added to the thermally expandable fire-resistant resin composition.

Description

  The present invention relates to a thermally expandable refractory resin composition.

Buildings and the like are provided with fire prevention compartments for the purpose of preventing the spread of fire and the spread of smoke due to fire. This fire compartment separates the space between rooms and the upper and lower floors so that even if a fire occurs in one fire compartment, the other fire compartment is not affected by the fire. ing.
However, there are places through which the flame, smoke, etc. can pass in the fire prevention compartment. Specifically, there are through holes or the like provided in the fire prevention compartment to allow piping to pass through the plurality of fire prevention compartments. In the event of a fire, there may be a problem of fire spread and smoke diffusion through the through-holes.
As a material corresponding to this problem, a thermally expandable refractory resin composition that forms an expansion residue by heat at the time of a fire has been studied.
If the molded body of this heat-expandable refractory resin composition is placed in the through hole or the like, the molded body expands due to heat at the time of a fire to form an expansion residue. For this reason, since a through-hole etc. can be obstruct | occluded with the expansion | swelling residue originating in the said molded object installed in the said through-hole etc. if a fire etc. generate | occur | produce, a fire spread and the spreading | diffusion of smoke can be prevented. .

As an example of the heat-expandable fire-resistant resin composition, a heat-expandable fire-resistant resin composition obtained by blending an elastomer, neutralized heat-expandable graphite, a phosphorus-containing compound, or the like has been proposed.
An elastomer foam having a closed cell structure obtained by molding this refractory resin composition is said to be excellent in heat insulation and fire resistance (Patent Document 1).
However, since moisture may permeate into the foam, there is a concern that the thermally expandable refractory resin composition containing a phosphorus-containing compound may be eluted by moisture derived from moisture, condensation, rainwater, and the like.
Since a molded body obtained by molding a thermally expandable refractory resin composition containing the phosphorus-containing compound is often placed in a building or the like for a long time, it is likely to be subject to a change in performance due to moisture.

As one means to prevent the influence of moisture, a thermally expandable refractory material containing a phosphorus-containing compound is molded, and a thermally expandable refractory piece obtained by pulverizing or chipping the molded material is mixed with an elastomer and molded. The technique to do is proposed (patent document 2).
According to this technique, the phosphorus-containing compound is confined inside the thermally expandable refractory piece, and a structure in which the elastomer is covered around the thermally expandable refractory piece is obtained. For this reason, the influence of the water | moisture content with respect to a phosphorus containing compound can be reduced.

  However, when an elastomer that easily absorbs moisture is selected as the elastomer, the moisture absorbed by the elastomer always comes into contact with the thermally expandable refractory piece, so that there still remains a problem that the phosphorus-containing compound is eluted.

  On the other hand, if the heat-expandable fire-resistant resin composition can be used for extrusion molding, the heat-expandable fire-resistant resin composition can be continuously formed. It becomes possible to manufacture the formed body efficiently.

As one of the prior arts related to extrusion molding of a resin composition containing thermally expandable graphite, it is formed of a resin composition containing 1 to 15 parts by weight of thermally expandable graphite with respect to 100 parts by weight of polyvinyl chloride. There has been proposed a multilayer fire-resistant piping material comprising a fire-resistant expansion layer and a coating layer formed of a polyvinyl chloride resin composition that does not contain a thermally expandable component (Patent Documents 3 and 4).
According to these prior arts, it is disclosed that a three-layer structure comprising a fireproof expansion layer, a coating layer inside the fireproof expansion layer, and a coating layer outside the fireproof expansion layer is obtained by three-layer coextrusion molding. .

In general, it is usually difficult to perform extrusion using a thermally expandable refractory resin composition that begins to expand when heated.
The shape of the multilayer structure molded body disclosed in the prior art is a cylinder. When the cross-sectional shape of the molded body is symmetrical with respect to the central axis in the extrusion direction, the molded body can be molded because heat is applied evenly.
However, it is the prior art previously shown whether or not a molded body having an appearance that can be used as a product is obtained when extrusion molding is performed using a thermally expandable refractory resin composition for a shape other than a cylinder. Then it is unknown.

WO2004 / 096369 JP 2005-220575 A JP 2008-180367 A JP 2008-180068 A

  An object of the present invention is to provide a thermally expandable refractory resin composition excellent in fire resistance, water resistance and moldability.

  As a result of intensive studies by the present inventors, a thermally expandable refractory resin composition comprising at least one selected from the group consisting of EPDM, polybutene and polybutadiene, and thermally expandable graphite, a boron-containing compound, an antimony-containing compound and a vulcanizing agent The present invention has been found to meet the object of the present invention, and the present invention has been completed.

That is, the present invention
[1] 100 parts by weight of resin component, 5 to 200 parts by weight of thermally expandable graphite, 20 to 200 parts by weight of boron-containing compound, 10 to 70 parts by weight of antimony-containing compound, and 0.1 to 10 parts by weight of vulcanizing agent ,
The resin component contains at least one selected from the group consisting of EPDM, polybutene and polybutadiene, and provides a thermally expandable refractory resin composition.

One of the present invention is
[2] The thermally expandable refractory resin composition according to the above [1], wherein the inorganic filler is contained in the range of 100 to 300 parts by weight with respect to 100 parts by weight of the resin component.

One of the present invention is
[3] The thermally expandable refractory resin composition according to the above [1] or [2], wherein the thermally expandable refractory resin composition includes two or more types of thermally expandable graphite having different thermal expansion start temperatures of 30 ° C. or more. It provides things.

One of the present invention is
[4] The thermally expandable refractory resin composition according to any one of [1] to [3], wherein the softening agent is contained in an amount of 20 to 200 parts by weight with respect to 100 parts by weight of the resin component. Is.

One of the present invention is
[5] The thermally expandable refractory resin composition according to any one of the above [1] to [4], wherein the foaming agent is contained in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin component. It is to provide.

One of the present invention is
[6] The thermally expandable refractory resin composition contains at least one selected from the group consisting of a heat stabilizer, a lubricant, a processing aid, an antioxidant, an antistatic agent, a pigment, a crosslinking agent, and a crosslinking accelerator. The thermally expandable refractory resin composition according to any one of the above [1] to [5] is provided.

A molded product obtained by molding the thermally expandable refractory resin composition according to the present invention is excellent in fire resistance, water resistance and moldability. For this reason, even if it is a molded product that has been used for a long time after molding the thermally expandable refractory resin composition according to the present invention, it is possible to prevent the performance from being deteriorated due to the influence of moisture, and thus maintains excellent fire resistance. can do.
Furthermore, it is possible to produce a molded article having excellent appearance by performing extrusion molding using the thermally expandable refractory resin composition according to the present invention.

  Further, when the thermally expandable refractory resin composition according to the present invention contains two or more kinds of thermally expandable graphite having different thermal expansion start temperatures of 30 ° C. or more, the molded body of the thermally expandable refractory resin composition has a fire or the like. The expansion residue can be formed from a relatively low temperature when exposed to the heat. Further, even when the temperature is further increased after forming the expansion residue, the expansion residue can be additionally formed, so that a molded article having excellent fire resistance can be provided.

Moreover, when the thermally expansible fireproof resin composition which concerns on this invention contains a foaming agent, the foaming molding which contains a bubble inside the molded object obtained can be obtained.
In the case of a foamed molded product obtained by molding a conventional thermally expandable refractory resin composition, when the foamed molded product is used in a place affected by moisture, the foamed molded product retains moisture. Because of its function, the foamed molded product has a problem that it is more susceptible to moisture.
On the other hand, in the case of the thermally expandable refractory resin composition according to the present invention, since it is excellent in water resistance, it is hardly affected by moisture, and excellent fire resistance can be maintained even if it is a foam molded article.

The thermally expandable refractory resin composition according to the present invention includes a resin component, thermally expandable graphite, a boron-containing compound, an antimony-containing compound, and a vulcanizing agent. First, the resin component used in the present invention will be described.
The resin component used in the present invention contains at least one selected from the group consisting of EPDM, polybutene and polybutadiene.
As said EPDM used for this invention, the terpolymer with ethylene, propylene, and the diene monomer for bridge | crosslinking is mentioned, for example.
The diene monomer for crosslinking used in the EPDM is not particularly limited. For example, 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene Cyclic dienes such as 2-norbornene, 5-isopropylidene-2-norbornene, norbornadiene,
1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl- Examples include chain non-conjugated dienes such as 1,7-octadiene.

The EPDM preferably has a Mooney viscosity (ML _{1 + 4} 100 ° C.) in the range of 35 to 100, more preferably in the range of 40 to 70.
When the Mooney viscosity is 35 or more, the flexibility is excellent. Further, when the Mooney viscosity is 100 or less, it can be prevented from becoming too hard.
The Mooney viscosity is a measure of viscosity measured by an EPDM Mooney viscometer.

The EPDM preferably has a crosslinking diene monomer content in the range of 2.0 wt% to 20 wt%, and more preferably in the range of 5.0 wt% to 15 wt%.
If it is 2.0% by weight or more, cross-linking between molecules proceeds, so that flexibility is excellent, and if it is 20% by weight or less, weather resistance is excellent.

  Moreover, as said polybutadiene, a commercial item can be selected suitably and can be used. Examples of such polybutadiene include homopolymer types such as Claprene LBR-305 (manufactured by Kuraray Co., Ltd.) and copolymers of 1,2-bonded butadiene and 1,4-bonded butadiene such as Poly bd (manufactured by Idemitsu Kosan Co., Ltd.) And a copolymer type of ethylene, 1,4-bonded butadiene, and 1,2-bonded butadiene such as Kuraprene L-SBR-820 (manufactured by Kuraray Co., Ltd.).

The polybutene preferably has a weight average molecular weight of 300 to 2000 as measured by a method based on ASTM D 2503.
When the weight average molecular weight is less than 300, since the viscosity is low, the polybutene tends to ooze out on the surface of the molded product after molding. On the other hand, if it exceeds 2000, the viscosity tends to be high and extrusion molding tends to be difficult.
Examples of the polybutene used in the present invention include “100R” (weight average molecular weight: 940), “300R” (weight average molecular weight: 1450) manufactured by Idemitsu Petrochemical Co., Ltd., “HV-100” (weight) manufactured by Nippon Petrochemical Co., Ltd. Average molecular weight: 970) and “H-100” (weight average molecular weight: 940) manufactured by AMOCO.

The resin component used in the present invention is preferably one in which at least one of polybutene and polybutadiene is added to EPDM from the viewpoint of improving moldability.
The addition amount of at least one of the polybutene and polybutadiene with respect to 100 parts by weight of the resin component is preferably in the range of 1 to 30 parts by weight, and more preferably in the range of 3 to 25 parts.

When the thermally expandable refractory resin composition according to the present invention is molded, a foaming agent may be used when bubbles are contained in the molded body.
Examples of the foaming agent include an azo compound-containing foaming agent, a nitroso compound-containing foaming agent, a sulfonyl / hydrazide-containing foaming agent, and a bicarbonate-containing foaming agent. Other examples include sodium bicarbonate, p-toluene sulfonyl semicarbazide, and microencapsulated blowing agent.

Examples of the azo compound-containing blowing agent include azodicarbonamide and barium azodicarboxylate.
Examples of the nitroso compound-containing foaming agent include N, N′-dinitrosopentamethylenetetramine.
Examples of the sulfonyl hydrazide-containing blowing agent include 4,4′-oxybis (benzenesulfonyl hydrazide), hydrazodicarbonamide, toluenesulfonyl hydrazide and the like.
Examples of the bicarbonate-containing foaming agent include sodium bicarbonate.

  The said foaming agent can use 1 type, or 2 or more types.

The microencapsulated foaming agent is one in which one or more of the foaming agents shown above are encapsulated in microcapsules. As the synthetic resin used for the microencapsulated foaming agent, for example, a thermoplastic synthetic resin that melts when it reaches a certain temperature or higher may be used.
When the thermally expandable refractory resin composition is heated to a certain temperature or higher by adding the microencapsulated foaming agent to the thermally expandable refractory resin composition according to the present invention, the synthesis is performed. Since the resin melts, the thermally expandable refractory resin composition can be foamed.

  The amount of the foaming agent used relative to the resin component is usually in the range of 0.1 to 20 parts by weight and preferably in the range of 1.0 to 10 parts by weight with respect to 100 parts by weight of the resin component.

Furthermore, when using the said foaming agent, a foaming adjuvant can also be used.
By using the foaming aid, the decomposition temperature of the foaming agent is lowered, and foaming can be performed more efficiently.
Examples of the foaming aid include organic amine, di-n-butylamine, aluminum sulfate, diethanolamine, urea, urea compound, salicylic acid, phthalic anhydride, benzoic acid, and diethylene glycol.
The amount of the foaming aid used for the EPDM is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component, for example.

  Each of the foaming aids can be used alone or in combination of two or more.

Next, the thermally expandable graphite used in the present invention will be described.
The heat-expandable graphite is a conventionally known substance, and powders such as natural scaly graphite, pyrolytic graphite, and quiche graphite are mixed with an inorganic acid such as concentrated sulfuric acid, nitric acid, and selenic acid, and concentrated nitric acid, perchloric acid, peroxygen, and the like. A graphite intercalation compound is produced by treatment with a strong oxidizing agent such as chlorate, permanganate, dichromate, or hydrogen peroxide. The heat-expandable graphite produced is a crystalline compound that maintains the layered structure of carbon.

The thermally expandable graphite used in the present invention can be neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like with respect to the thermally expandable graphite obtained by the acid treatment. .
Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine.
Examples of the alkali metal compound and alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium, and magnesium, oxides, carbonates, sulfates, and organic acid salts.
Specific examples of the thermally expandable graphite used in the present invention include “CA-60S” manufactured by Nippon Kasei Co., Ltd.

If the particle size of the thermally expandable graphite is too fine, the degree of expansion of the graphite is small, and the foamability tends to decrease. Further, if it becomes too large, there is an effect in that the degree of expansion is large, but when kneaded with a resin, the dispersibility is poor and the moldability is lowered, and the mechanical properties of the obtained extruded product tend to be lowered. .
For this reason, the particle size of the thermally expandable graphite is preferably in the range of 20 to 200 mesh.

If the amount of the thermally expansive graphite added decreases, the fire resistance and foamability tend to decrease. Moreover, when it increases, it will become difficult to extrusion-mold, the surface property of the obtained molded object will worsen, and there exists a tendency for a mechanical physical property to fall. For this reason, the addition amount of the said thermally expansible graphite with respect to 100 weight part of said resin components is the range of 5-200 weight part.
The amount of the thermally expandable graphite added is preferably in the range of 10 to 150 parts by weight.

In the present invention, it is preferable to use two or more kinds of thermally expandable graphites having different expansion start temperatures of 30 ° C. or more.
Here, the expansion start temperature means a temperature at which the expansion of the thermally expandable graphite can be observed when the thermally expandable graphite is heated, and can be measured by mechanical thermal analysis (TMA).
The expansion start temperature of the thermally expandable graphite used in the present invention can be appropriately selected and used within the range of 150 ° C. to 400 ° C., but when using two or more types of thermally expandable graphite, Within this temperature range, those having an expansion start temperature different by 30 ° C. or more can be selected and used.

When a thermally expandable graphite having a high expansion start temperature is used for a molded product of the thermally expandable refractory resin composition according to the present invention, an expansion residue having a sufficient volume is formed when heat such as fire is not transmitted to the molded body. In some cases, the fire resistance expected of the molded body may not be exhibited.
If heat-expandable graphite having a low expansion start temperature is used, the fire resistance expected of the molded body can be exhibited.

However, problems also arise when using thermally expandable graphite having a low expansion start temperature.
In the case of the molded body using thermally expandable graphite having a low expansion start temperature, an expansion residue is formed at a relatively low temperature. When the formation of this expansion residue is completed, due to the heat of a fire or the like, the metal building material in the vicinity of the expansion residue, a wall or the like is deformed and a gap is generated around the expansion residue. Flames and smoke will leak from the gap.

By adopting two or more types of thermally expandable graphite having different expansion start temperatures of 30 ° C. or more, heat expandable graphite having a relatively low expansion start temperature can be obtained even at a stage where the heat of a fire or the like is hardly transmitted and the molded body is not sufficiently heated. An expansion | swelling residue can be formed and the clearance gap around the building materials in which the said molded object was installed can be obstruct | occluded.
Further, when the temperature of the expansion residue rises, the thermally expansive graphite having a relatively high expansion start temperature can additionally form the expansion residue, so that the gap near the expansion residue can be added more reliably. It can be occluded by the expansion residue formed.

Next, the boron-containing compound used in the present invention will be described.
Examples of the boron-containing compound used in the present invention include boron compounds such as boric acid, metaboric acid, orthoboric acid, hypoboric acid, boronic acid, borinic acid, and diboron trioxide,
Zinc borate, zinc metaborate, ortho orthoborate, zinc hypoborate, zinc boronate, zinc borate, calcium borate, calcium metaborate, calcium orthoborate, calcium hypoborate, calcium boronate, calcium borate, boron Sodium phosphate, sodium metaborate (borax), sodium orthoborate, sodium hypoborate, sodium boronate, sodium borate, potassium borate, potassium metaborate, potassium orthoborate, potassium hypoborate, potassium boronate, borin Examples thereof include boron-containing salts such as potassium acid, cobalt metaborate, barium metaborate, and ammonium metaborate.

From the viewpoint of handleability, the boron-containing compound used in the present invention is preferably a boric acid-containing salt.
One or two or more of the boron-containing compounds can be used.

When the addition amount of the boron-containing compound is decreased, the expansion during heating tends to be reduced. Moreover, when it increases, there exists a tendency for it to become difficult to shape | mold. For this reason, the addition amount of the said boron containing compound with respect to 100 weight part of said resin components is the range of 20-200 weight part.
The amount of boron compound added is preferably in the range of 30 to 180 parts by weight.

Next, the antimony-containing compound used in the present invention will be described.
Examples of the antimony-containing compound used in the present invention include antimony oxide, antimonate, pyroantimonate, and the like.
Examples of the antimony oxide include antimony trioxide and antimony pentoxide.
Examples of the antimonate include sodium antimonate and potassium antimonate.
Examples of the pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

  The antimony-containing compound used in the present invention is preferably antimony trioxide.

  The said antimony containing compound can use 1 type, or 2 or more types.

When the amount of the antimony-containing compound is decreased, the flame retardancy tends to decrease. Moreover, when it increases, there exists a tendency for it to become difficult to shape | mold. For this reason, the addition amount of the antimony-containing compound with respect to 100 parts by weight of the resin component is in the range of 10 to 70 parts by weight.
The addition amount of the antimony-containing compound is preferably in the range of 15 to 60 parts by weight.

Next, the vulcanizing agent used in the present invention will be described.
Examples of the vulcanizing agent include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate, and the like.
The vulcanizing agent is preferably sulfur or tetramethylthiuram disulfide.

  The said vulcanizing agent can use 1 type, or 2 or more types.

When the amount of the vulcanizing agent is decreased, the stability during heating tends to be lowered. Moreover, when it increases, there exists a tendency for it to become difficult to shape | mold. For this reason, the addition amount of the vulcanizing agent with respect to 100 parts by weight of the resin component is in the range of 0.1 to 10 parts by weight.
The addition amount of the vulcanizing agent is preferably in the range of 0.5 to 5 parts by weight.

When using the vulcanizing agent, a vulcanization accelerator can be used in combination.
Examples of the vulcanization accelerator include thiazole-containing vulcanization accelerator, guanidine-containing vulcanization accelerator, aldehyde amine-containing vulcanization accelerator, imidazoline-containing vulcanization accelerator, thiourea-containing vulcanization accelerator, and thiuram-containing vulcanization accelerator. , Dithioate-containing vulcanization accelerators, thiourea-containing vulcanization accelerators, xanthate-containing vulcanization accelerators, and the like.

  Examples of the thiazole-containing vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, and the like.

  Examples of the guanidine-containing vulcanization accelerator include diphenyl guanidine and triphenyl guanidine.

  Examples of the aldehyde amine-containing vulcanization accelerator include an acetaldehyde / aniline condensate.

  Examples of the imidazoline-containing vulcanization accelerator include 2-mercaptoimidazoline.

  Examples of the thiourea-containing vulcanization accelerator include diethyl thiourea and dibutyl thiourea.

  Examples of the thiuram-containing vulcanization accelerator include tetramethylthiuram monosulfide and tetramethylthiuram disulfide.

  Examples of the dithioate-containing vulcanization accelerator include zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate.

Examples of the thiourea-containing vulcanization accelerator include ethylene thiourea and N, N′-diethylthiourea.

  Examples of the xanthate-containing vulcanization accelerator include zinc dibutylxatogenate.

  The said vulcanization accelerator can use 1 type, or 2 or more types.

The amount of the vulcanization accelerator added to 100 parts by weight of the resin component is preferably in the range of 0.1 to 20 parts by weight. By using the vulcanization accelerator, vulcanization can proceed efficiently.
The addition amount of the vulcanization accelerator is preferably in the range of 0.1 to 10 parts by weight.

When the vulcanizing agent is used, a vulcanization aid can be used in combination.
Examples of the vulcanization aid include quinone dioxime vulcanization aids such as p-quinonedioxime, acrylic-containing vulcanization aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate,
Allyl-containing vulcanization aids such as diallyl phthalate and triallyl isocyanurate, maleimide-containing vulcanization aids,
Examples include divinylbenzene, zinc oxide, magnesium oxide, and zinc white.

  The amount of the vulcanization aid added to 100 parts by weight of the resin component is preferably in the range of 1 to 50 parts by weight. By using the vulcanization aid, vulcanization can be efficiently advanced.

Next, the thermally expandable refractory resin composition according to the present invention can contain an inorganic filler.
Examples of the inorganic filler include metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites,
Hydrous minerals such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate,
Calcium salts such as calcium sulfate, gypsum fiber, calcium silicate,
Silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black , Graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash Etc.
The inorganic filler used in the present invention is preferably a metal oxide, a hydrous inorganic substance, or a metal carbonate.

  The water-containing inorganic substance generates water by a dehydration reaction at the time of heating, an endotherm is generated by this water, a temperature rise is reduced, and high heat resistance is obtained, and an oxide remains as a heating residue, which is an aggregate. It is preferable from the point that the strength of the foamed refractory obtained by expanding and carbonizing the refractory resin composition is improved.

  Among the water-containing inorganic substances, magnesium hydroxide and aluminum hydroxide have different temperature ranges in which the dehydration effect is exerted, so the combined use of both increases the temperature range in which the dehydration effect is exerted, and more effective suppression of temperature rise. Since an effect is acquired, it is preferable to use magnesium hydroxide and aluminum hydroxide together.

  The metal carbonate is preferable in that the oxide remains as a heating residue and this acts as an aggregate, so that the strength of the foamed refractory obtained by expanding and carbonizing the refractory resin composition is improved.

  The said inorganic filler may be used independently or 2 or more types may be used together. The inorganic filler is preferably a combination of the hydrated inorganic substance and a metal carbonate. The water-containing inorganic substance and the metal carbonate are considered to contribute to the improvement of the strength of the combustion residue and the increase of the heat capacity because they function as an aggregate.

  The average particle size of the inorganic filler is preferably 0.5 to 100 μm, and more preferably 1 to 50 μm. If the average particle size of the inorganic filler is small, the inorganic filler aggregates and it becomes difficult to uniformly disperse it in the refractory resin composition. When the average particle size of the inorganic filler is large, the mechanical strength of the refractory resin composition is lowered.

  The inorganic filler is preferably used in combination of a large particle size and a small particle size, and the combined use of the inorganic filler maintains the mechanical strength of the thermally expandable refractory resin composition. An inorganic filler can be contained in the thermally expandable refractory resin composition at a high concentration.

  When the amount of the inorganic filler added is small, the fluidity of the thermally expandable refractory resin composition tends to be improved. Moreover, when it increases, there exists a tendency for the intensity | strength of the molded object of the said thermally expansible fireproof resin composition to improve. Therefore, the amount of the inorganic filler added to 100 parts by weight of the resin component is preferably in the range of 10 to 300 parts by weight, and more preferably in the range of 50 to 150 parts by weight.

Moreover, a softening agent can be used for the heat-expandable refractory resin composition used in the present invention.
The softener is not particularly limited as long as it is a softener generally used when producing a thermoplastic resin molded article. Specifically, for example, phthalate ester softeners such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), diisodecyl phthalate (DIDP),
Fatty acid ester softeners such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA);
Epoxidized ester softeners such as epoxidized soybean oil,
Polyester softeners such as adipic acid ester and adipic acid polyester,
Trimellitic acid ester softeners such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM),
Phosphate ester softeners such as trimethyl phosphate (TMP) and triethyl phosphate (TEP)
Examples include process oils such as mineral oil.
The softener can be used alone or in combination of two or more.

  When the addition amount of the softening agent decreases, the extrusion moldability tends to decrease, and when the addition amount increases, the obtained molded body tends to be too soft. For this reason, it is preferable that the addition amount of the softening agent is in the range of 20 to 200 parts by weight with respect to 100 parts by weight of the thermally expandable refractory resin composition.

  Further, when the thermally expandable refractory resin composition used in the present invention contains a phosphorus compound excluding a phosphate ester softener, the extrusion moldability is lowered. For this reason, it is preferable not to contain the phosphorus compound except a phosphate ester softening agent. In addition, the phosphate ester softening agent which is the softening agent demonstrated previously can be contained.

Phosphorus compounds that inhibit extrusion moldability are as follows.
Red phosphorus,
Various phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate,
Metal phosphates such as sodium phosphate, potassium phosphate, magnesium phosphate,
Ammonium polyphosphates,
Examples thereof include compounds represented by the following chemical formulas.

上記化学式中、Ｒ^１及びＲ^３は、水素、炭素数１〜１６の直鎖状若しくは分岐状のアルキル基、又は、炭素数６〜１６のアリール基を表す。

In the above chemical formula, R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.

R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon. The aryloxy group of Formula 6-16 is represented.

  Examples of the compound represented by the chemical formula include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2, 3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid , Diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid and the like.

The ammonium polyphosphates are not particularly limited, and examples thereof include ammonium polyphosphate and melamine-modified ammonium polyphosphate.
In the present invention, these phosphorus compounds that inhibit extrusion molding are not used.

  In addition, the thermally expandable refractory resin composition used in the present invention is generally used as necessary, as long as it does not impair its physical properties, heat stabilizers other than phosphorus compounds, lubricants, processing aids, Antioxidants, antistatic agents, pigments, crosslinking agents, crosslinking accelerators, and the like may be added.

Examples of the heat stabilizer include lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, and dibasic lead stearate.
Organotin heat stabilizers such as organotin mercapto, organotin malate, organotin laurate, dibutyltin malate,
Examples thereof include metal soap heat stabilizers such as zinc stearate and calcium stearate.
One or two or more heat stabilizers can be used.

Examples of the lubricant include waxes such as polyethylene, paraffin, and montanic acid,
Various ester waxes,
Organic acids such as stearic acid, ricinoleic acid,
Organic alcohols such as stearyl alcohol,
Examples include amide compounds such as dimethylbisamide.
The said lubricant can use 1 type, or 2 or more types.

  Examples of the processing aid include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, and high molecular weight polymethyl methacrylate.

  As said antioxidant, a phenol compound etc. are mentioned, for example.

  Examples of the antistatic agent include amino compounds.

  Examples of the pigment include inorganic pigments such as organic pigments such as azos, phthalocyanines, slenes, and dye lakes, oxides, molybdenum chromates, carbon black, sulfides / selenides, and ferrocyanides. And pigments.

  Examples of the crosslinking agent include sulfur. Examples of the crosslinking accelerator include tellurium diethyldithiocarbamate, N, N, N ′, N′-tetraethylthiuram disulfide, benzyl diethyldithiocarbamate, and the like.

[Specific Examples of Thermally Expandable Refractory Resin Composition]
Specific examples of the thermally expandable refractory resin composition used in the present invention are as follows.
(A) Resin composition comprising a resin component, thermally expandable graphite, boron-containing compound, antimony-containing compound and vulcanizing agent (b) Resin component, thermally expandable graphite, boron-containing compound, antimony-containing compound, vulcanizing agent and Resin composition comprising inorganic filler (c) Resin component, thermally expandable graphite, boron-containing compound, antimony-containing compound, vulcanizing agent, resin composition comprising inorganic filler and softener (d) Resin component, thermal expansion Resin composition comprising conductive graphite, boron-containing compound, antimony-containing compound, vulcanizing agent, inorganic filler, softener and foaming agent (e) at least one resin selected from the group consisting of (a) to (d) above For the composition, selected from the group consisting of heat stabilizers, lubricants, processing aids, foaming aids, vulcanization accelerators, vulcanization aids, antioxidants, antistatic agents, pigments, crosslinking agents and crosslinking accelerators. Little Resin composition prepared by adding one Kutomo

The heat-expandable refractory resin composition according to the present invention is known from the resin component, heat-expandable graphite, boron-containing compound, antimony-containing compound and vulcanizing agent, and other additives contained as necessary. It can be obtained by melt-kneading using a kneader.
In addition, as a kneading apparatus, an extruder, a kneader mixer, a two roll, a Banbury mixer etc. are mentioned, for example.
The heat-expandable refractory resin composition can be molded by a method such as casting the obtained heat-expandable refractory resin composition into a mold.
The molded object obtained by shape | molding the thermally expansible fireproof resin composition which concerns on this invention can be preferably used for the use of a thermally expansible packing material.
More preferably, the thermally expandable packing material is made of a foamed molded article containing bubbles inside.

  The present invention is described in detail below based on examples, but the present invention is not limited to the following examples.

EPDM (EPDM with Mooney viscosity (ML _{1 + 4} 100 ° C.) of 42, (ML _{1 + 4} 125 ° C.) of 59 and diene content of 10%. Sumitomo Chemical Co., Ltd., trade name “Esprene 505”) 100 parts by weight, thermal expansibility 60 parts by weight of graphite (trade name “CA-60” manufactured by Nippon Kasei Co., Ltd., thermal expansion start temperature 200 ° C.), 2 parts by weight of carbon, 32 parts by weight of softening agent, 1 part by weight of stearic acid, 7 parts by weight of zinc oxide, calcium carbonate 80 parts by weight (trade name “BF300” manufactured by Bihoku Flour Chemical Co., Ltd., average particle size: 8 μm), 60 parts by weight of zinc borate (manufactured by Showa Chemical Co., Ltd.), 20 parts by weight of antimony trioxide, sulfur (“sulfur manufactured by Tsurumi Chemical Co., Ltd.) ] 6 parts by weight and 1 part by weight of a vulcanization accelerator were fed to a kneader, melted and kneaded, and a sheet-like thermally expandable refractory resin composition having a thickness of 2 mm was obtained by calendering.

[Performance comparison test]
1. The thickness T ₁ of the study the sheet-like thermally expandable fireproof resin composition of expansion ratio was measured.
Next, the sheet-like thermally expandable refractory resin composition was heated in an electric furnace at 600 ° C. for 30 minutes to obtain a residue after combustion.
The thickness T ₂ of the residue after the combustion was measured to calculate the expansion ratio on the basis of the following equation.
Expansion ratio (%) = 100 × thickness T ₂ of the foamed refractory layer / thickness T ₁ of the refractory resin composition
The results are shown in Table 1.

2. Residual hardness test after combustion A 0.25 cm ² indenter was pressed at a speed of 0.1 cm / second on the post-combustion residue obtained by measurement of the expansion ratio using a micro compression tester. The residue was compressed and the stress at break was measured.
The results are shown in Table 1.

3. Water resistance test ○ When the sheet-like thermally expandable fire-resistant resin composition was immersed in water at room temperature and the eluate could not be observed with the naked eye, the eluate could be observed with the naked eye The case was marked with x.
The results are shown in Table 1.

4). Moldability test The sheet-like thermally expandable refractory resin composition is supplied to an extrusion molding machine, and is melted at 130 to 170 ° C. in an extruder such as a single screw extruder or a twin screw extruder according to a conventional method. Carried out.
A heat-expandable refractory resin composition having the composition shown in Table 1 is prepared, and each heat-expandable refractory resin composition is supplied to a single screw extruder (65 mm extruder manufactured by Ikekai Kikai Co., Ltd.) and extruded at a pressure of 150 t. By performing the above, a sheet-like molded product having a thickness of 2 mm and a thickness of 1 mm was extruded at a speed of 1 m / hr.
Regarding the thickness accuracy of the sheet-like molded product, ○ when the thickness accuracy is plus or minus 0.2 mm or less, Δ when plus or minus 0.2 mm and plus or minus 0.4 mm or less, and plus or minus 0.4 mm. The case was marked with x. The results are also shown in Table 1.

In the case of Example 1, except that the amount of the heat-expandable graphite used was changed from 60 parts by weight to 30 parts by weight, and 5 parts by weight of the foaming agent and the foaming aid were used, respectively. The experiment was conducted in the same manner.
The results are shown in Table 1.

In the case of Example 1, the amount of thermally expandable graphite used was changed from 60 parts by weight to 150 parts by weight, the amount of softener used was changed from 32 parts by weight to 55 parts by weight, and stearic acid was added. Not used, changed the amount of calcium carbonate used from 80 parts by weight to 10 parts by weight, changed the amount of zinc borate used from 60 parts by weight to 180 parts by weight, and used antimony trioxide The experiment was performed in the same manner as in Example 1 except that the amount of was changed from 20 parts by weight to 60 parts by weight.
The results are shown in Table 1.

In the case of Example 1, the amount of thermally expandable graphite used was changed from 60 parts by weight to 10 parts by weight, the amount of zinc borate used was changed from 60 parts by weight to 40 parts by weight, a foaming agent An experiment was conducted in the same manner as in Example 1 except that 5 parts by weight of each of the foaming aids were used.
The results are shown in Table 1.

In the case of Example 1, the amount of thermally expandable graphite used was changed from 60 parts by weight to 5 parts by weight, the amount of zinc borate used was changed from 60 parts by weight to 35 parts by weight, and used. An experiment was conducted in the same manner as in Example 1 except that the amount of antimony trioxide was changed from 20 parts by weight to 15 parts by weight, and that 5 parts by weight of each of the foaming agent and the foaming aid were used.
The results are shown in Table 1.

In the case of Example 2, the experiment was performed in the same manner as in Example 2 except that 5 parts by weight of polybutadiene (manufactured by Ube Industries, trade name “BR150”) was added and used.
The results are shown in Table 1.

In the case of Example 2, an experiment was performed in the same manner as in Example 2 except that 20 parts by weight of polybutadiene (manufactured by Ube Industries, trade name “BR150”) was added.
The results are shown in Table 1.

In the case of Example 2, instead of 30 parts by weight of thermally expandable graphite having a thermal expansion start temperature of 200 ° C., 15 parts by weight of thermally expandable graphite having a thermal expansion start temperature of 200 ° C. and having a thermal expansion start temperature of 300 ° C. The experiment was performed in the same manner as in Example 2 except that 15 parts by weight of thermally expandable graphite (trade name “STZR-503” manufactured by Sanyo Trading Co., Ltd.) was used.
The results are shown in Table 1.

[Comparative Example 1]
In the same manner as in Example 1, except that zinc borate and antimony trioxide were not used and ammonium polyphosphate (trade name “AP422” manufactured by Clariant Co., Ltd.) was used in an amount of 80 parts by weight. Went.
The results are shown in Table 1.

[Comparative Example 2]
In the same manner as in Example 2, except that zinc borate and antimony trioxide were not used and ammonium polyphosphate (trade name “AP422”, manufactured by Clariant) was used in an amount of 80 parts by weight. Went.
The results are shown in Table 1.

In the case of Examples 2, 4, 5, and 6 to 8, a foaming agent and a foaming aid were used. By using the foaming agent and the foaming aid, air bubbles can be included in the sheet-like molded product obtained by extrusion molding.
Since the sheet-like molded product containing bubbles is small in density and excellent in flexibility, it is shown in Reference Examples 2, 4, 5, 6 to 8 as a thermally expandable refractory resin composition used in each of the following examples. Each thermally expandable resin composition particle is excellent. In particular, when EPDM and polybutadiene are used in combination as resin components, excellent performance is exhibited.
If the density of the heat-expandable refractory resin composition layer obtained by molding the heat-expandable refractory resin composition used in the present invention is in the range of 0.1 to 0.8 g / cm ³ , it is flexible. It is more preferable because of its excellent properties.

As is clear from the comparison of Examples 1 to 8 and Comparative Examples 1 and 2, when a phosphorus-containing compound is used, the obtained heat-expandable refractory resin composition is inferior in water resistance.
On the other hand, the heat-expandable fireproof resin composition according to the present invention is particularly excellent in water resistance since it contains a boron-containing compound and an antimony-containing compound.
Moreover, it is excellent in moldability.

  Since the thermally expandable refractory resin composition according to the present invention is excellent in water resistance, fire resistance and moldability, the molded body formed by molding the thermally expandable refractory resin composition is exposed to a humid place and water. It can be applied to the usage that is installed in the place.

Claims (6)

100 parts by weight of resin component, 5 to 200 parts by weight of thermally expandable graphite, 20 to 200 parts by weight of boron-containing compound, 10 to 70 parts by weight of antimony-containing compound and 0.1 to 10 parts by weight of vulcanizing agent,
The thermally expandable refractory resin composition, wherein the resin component contains at least one selected from the group consisting of EPDM, polybutene, and polybutadiene.   The thermally expandable refractory resin composition according to claim 1, wherein the inorganic filler is contained in an amount of 100 to 300 parts by weight with respect to 100 parts by weight of the resin component.  The heat-expandable refractory resin composition according to claim 1 or 2, wherein the heat-expandable refractory resin composition includes two or more kinds of heat-expandable graphite having different thermal expansion start temperatures of 30 ° C or more.   The thermally expandable refractory resin composition according to any one of claims 1 to 3, wherein the softening agent is contained in a range of 20 to 200 parts by weight with respect to 100 parts by weight of the resin component.   The thermally expandable refractory resin composition according to any one of claims 1 to 4, wherein the foaming agent is contained in a range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin component.   The thermally expandable refractory resin composition contains at least one selected from the group consisting of a thermal stabilizer, a lubricant, a processing aid, an antioxidant, an antistatic agent, a pigment, a crosslinking agent, and a crosslinking accelerator. The heat-expandable refractory resin composition according to any one of 1 to 5.