JP2002129025A - Foamable fireproof composition with water-resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamable fireproof composition with water-resistance which makes the combustibles fireproof by forming an expanded and foamed carbonized layer by heating or which prevents smoke, flame or gases or the like generated by the combustion from flowing out to the outside. SOLUTION: The composition is obtained by containing (A) a thermoplastic resin and/or rubber material, (B) a phosphorous compound, (C) a heat expandable graphite, (D) a plasticizer, (E) an inorganic filler, (F) a polyfunctional alcohol and (G) an amino group-containing compound. The composition contains the component (A) of 50-85 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-resistant foam type fire-retardant composition.

[0002]

2. Description of the Related Art Heretofore, beams, steel columns, partition walls and the like of a building have been coated with a fire-resistant material in order to enhance the fire protection performance of the building. The current refractory coating is mainly sprayed with a semi-wet refractory material (such as rock wool). However, according to this method, the material is liable to be scattered at the time of work, and curing is required for its prevention, and problems such as work at high places have been left in terms of work surface safety. As means for solving these problems, various fireproof / fireproof sheets made of an inorganic compound such as ceramic and a nonwoven fabric have been proposed.
However, in areas with mobility around openings such as doors,
These fireproof and fireproof sheets were not suitable for use because of their poor elasticity and extremely poor displacement followability.

[0003] Japanese Patent Application Laid-Open No. 9-227716 discloses that
There has been proposed a fire-resistant resin composition having a heat expansion property comprising a thermoplastic resin, a phosphorus compound, neutralized heat-expandable graphite, and an inorganic filler. Such a resin composition can be formed into a sheet and can be easily coated with a fireproof coating.However, a large amount of the inorganic filler added to maintain the shape of the carbonized layer expanded and heated by heating gradually absorbs moisture, The shape retention is gradually reduced by the moisture and water. In the fire-resistant resin composition having such a thermal expansion property, if the shape of the foamed carbonized layer is not maintained, the fire resistance is significantly impaired. Therefore, the fire resistance of such a resin composition is water resistance and / or weather resistance. There was also a problem in terms of gender.

On the other hand, Japanese Patent Application Laid-Open No.
JP-A-109377 proposes a foamable refractory coating thermoplastic resin composition in which a phosphoric acid anhydride or a phosphate and, if necessary, a carbon-based material and a nonflammable gas generating material are blended with a thermoplastic resin. However, the composition disclosed herein has an insufficient level of water resistance and cannot meet the demand as a building material.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, it is an object of the present invention to (1) easily form into a sheet, and (2) expand and foam by heating to be strong. By forming a stable carbonized layer, combustibles are prevented,
(3) Even when foaming is performed after immersion in water or exposure to a humid atmosphere, the expansion ratio does not decrease as compared with those not immersed in water or exposure to a humid atmosphere, and the foamed carbonized An object of the present invention is to provide a foam-type fire-retardant composition in which the shapes of layers do not differ.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a phosphorus compound and a heat-expandable graphite are mixed in a thermoplastic resin and / or a rubber material at a specific ratio. As a result, a foamed fire-retardant composition having excellent flexibility, foamability, strength and workability, and water resistance has been obtained. That is, the present invention is a foamed fire-retardant composition comprising (A) a thermoplastic resin and / or a rubber-based material, (B) a phosphorus compound, and (C) thermally expandable graphite,
The present invention relates to a foamed fire-resistant resin composition containing 50 to 85% by weight of the thermoplastic resin and / or rubber-based material (A) in the composition. The present invention is also a foamed fire-retardant composition further comprising (D) a plasticizer, wherein the thermoplastic resin and / or rubber-based material of (A) and the plasticizer of (D) are in a total amount of 55-8.
It is preferable to contain 5% by weight in the composition. Also,
The present invention can further contain at least one of (E) an inorganic filler, (F) a polyfunctional alcohol, and (G) an amino group-containing compound.

The thermoplastic resin and / or rubber-based material (A) is preferably a polymer having at least one polymer chain obtained by polymerizing a monomer composed of an olefin-based compound.

Further, the present invention relates to a foamable fire-retardant composition wherein the thermoplastic resin (A) is a block copolymer comprising an aromatic vinyl compound unit and an olefin compound unit. The olefinic compound unit is preferably a compound unit mainly composed of isobutylene.

[0009] The rubber-based material (A) is preferably butyl rubber. The plasticizer (D) is preferably polybutene and poly-α-olefin.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The thermoplastic resin of the present invention is not particularly limited, for example, polyolefins such as polypropylene and polyethylene, polystyrene resin, ABS resin, MBS, acrylic resin, polyurethane resin, polyvinyl chloride resin, polyester resin, At least one selected from the group consisting of polyamide resins, polyphenylene ether resins, polycarbonate resins, poly (1-) butene resins, polypentene resins, block copolymers such as styrene-isoprene-styrene, etc. used. The thermoplastic resin is not particularly limited, but is preferably a polymer having at least one polymer chain obtained by polymerizing a monomer composed of an olefin compound having a high carbonized layer forming power. Examples of the olefin compound include ethylene, propylene, butene, pentene, hexene, octene, isobutylene, isopentene, butadiene, isoprene and the like.

Further, from the viewpoint of processability and sheet flexibility, a block copolymer composed of a block composed of an aromatic vinyl compound and a block composed of an olefin compound is more preferable. When such a block copolymer is used,
The sheet is flexible and can be easily deformed, and it is easy to cover a complicated shape. The block made of an aromatic vinyl compound is
50% by weight or more, preferably 7% by weight of the aromatic vinyl compound
The block occupies 0% by weight or more, more preferably 90% by weight or more. The block composed of an olefin compound refers to a block in which the olefin compound accounts for 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more.

The aromatic vinyl compound is not particularly restricted but includes, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, indene and the like. Is mentioned. Among the above compounds, styrene, α-methylstyrene, p-methylstyrene, and indene are preferred from the balance of cost, physical properties, and productivity, and two or more of them may be selected.

The olefinic compound is not particularly limited, and examples thereof include olefinic compounds having 1 to 6 carbon atoms such as ethylene, propylene, 1-butylene, isobutylene, butadiene and isoprene.
More than one species may be selected. Further, specific examples of the block composed of the olefinic compound obtained from the above compound include polybutadiene block, polyisoprene block, and hydrogenated polyethylene / butylene block, polyethylene / propylene block, and polyisobutylene block. Can be Among these, a polyisobutylene block containing a large amount of tertiary carbon necessary for forming a stable and strong carbonized layer is particularly preferable. The polyisobutylene block refers to a block mainly composed of isobutylene, that is, a block in which isobutylene accounts for 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more.

As the block copolymer formed from the block composed of the aromatic vinyl compound and the block composed of the olefin compound, any block copolymer having any structure can be used. Therefore, a triblock having a structure of (block composed of an aromatic vinyl compound-block composed of an olefin-based compound-block composed of an aromatic vinyl-based compound),
A diblock having a structure of (a block composed of an olefin-based compound-a block composed of an aromatic vinyl-based compound) or a mixture thereof is preferable.

The ratio of the olefin compound and the aromatic vinyl compound in the block copolymer formed from the block composed of the aromatic vinyl compound and the block composed of the olefin compound is not particularly limited. In view of the balance, 95 to 20 parts by weight of the olefin compound and 5 to 80 parts by weight of the aromatic vinyl compound are preferable, and 90 to 60 parts by weight of the olefin compound and 10 to 40 parts by weight of the aromatic vinyl compound are more preferable.

The number average molecular weight of the block copolymer formed from the block composed of the aromatic vinyl compound and the block composed of the olefinic compound is not particularly limited, but is preferably from 30,000 to 500,000.
00 to 400,000 is particularly preferred. When the number average molecular weight is less than 30,000, mechanical properties and the like are not sufficiently exhibited, and when the number average molecular weight exceeds 500,000, the moldability and the like are greatly reduced.

The rubber-based material of the present invention is not particularly restricted but includes, for example, natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, chloroprene rubber,
At least one selected from the group consisting of nitrile rubber, silicone rubber, styrene-butadiene rubber, ethylene-propylene rubber, butyl rubber and chlorinated butyl rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, fluorine rubber, urethane rubber, and the like. Seeds are used. Among these rubber-based materials, there is no particular limitation, and it is preferable that the polymer is a polymer having at least one polymer chain obtained by polymerizing a monomer composed of an olefin-based compound having a high carbonized layer forming power. ethylene,
Propylene, butene, pentene, hexene, octene,
Isobutylene, isopentene, butadiene, isoprene and the like. Particularly preferred are butyl rubber, chlorinated butyl rubber containing halogen and high flame retardancy, and chloroprene rubber. These thermoplastic resins and / or rubber-based materials may be used alone or in combination of two or more.

The amount of the component (A) contained in the foam type fire-retardant composition is 50 to 85% by weight, preferably 55 to 7% by weight.
It is 5% by weight, more preferably 60 to 70% by weight.
When the amount of the component (A) is 50% by weight or less, the water resistance decreases, and when it is 85% by weight or more, a good foamed state cannot be realized, and a good foam cannot be obtained.

As the component (B) of the present invention, a phosphorus compound is used. The phosphorus compound is not particularly limited, and may be at least one selected from the group consisting of red phosphorus, a phosphate compound, a polyphosphate compound, a phosphate, a polyphosphate, a phosphate amide, and a polyphosphate amide. use. The polyphosphoric acid is not particularly limited as long as phosphoric acid is condensed.
A 00 mer is preferred. These phosphorus compounds act as a catalyst for dehydrating organic substances in a heated environment, and also have a function of forming a nonflammable inorganic phosphoric acid film. Among the above phosphorus compounds, a salt compound of phosphoric acid or polyphosphoric acid and an amide compound of phosphoric acid or polyphosphoric acid are preferable. As a salt compound of phosphoric acid or polyphosphoric acid,
A salt of phosphoric acid or polyphosphoric acid with ammonia or an organic base is preferred, a salt of phosphoric acid or polyphosphoric acid with ammonia or an amine compound is more preferred, and ammonium polyphosphate or a derivative thereof is particularly preferred. Examples of the amine compound forming the salt include methylamine, ethylamine, and melamine, and a melamine salt of polyphosphoric acid is particularly preferable. As the amide compound of phosphoric acid or polyphosphoric acid, phosphoric acid or polyphosphoric acid melamineamide is particularly preferred. When a salt or amide with phosphoric acid or ammonium polyphosphate or amine reaches a decomposition temperature by heating, phosphoric acid and condensed phosphoric acid are generated by deamination such as deammonification. This acid acts as a catalyst for dehydrating organic substances and carbonizes the organic substances, resulting in formation of a fire-resistant carbonized layer. In addition, the ammonia gas, nitrogen gas, and the like generated at this time act as a foaming agent to expand the entire composition, and also reduce the oxygen concentration to suppress combustion. The phosphorus compound used in the present invention preferably has a phosphorus content of 10% by weight or more, a nitrogen content of 9% by weight or more, and a decomposition temperature of 200 ° C. or more. Such a salt or amide with phosphoric acid or ammonium polyphosphate or amine is not particularly limited. For example, an insolubilized polymer phosphorus compound made of Sumitomo Chemical Co., Ltd. (trade name “Sumisafe PM”) consisting of ammonium polyphosphate "), Coated ammonium polyphosphate (trade name" TERAGE C60 ") manufactured by Chisso Corporation.

The amount of the component (B) contained in the foam type fire-retardant composition is 1 to 44% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight. (A)
When the amount of the component is 1% by weight or less, formation of a carbonized layer is insufficient, and a good foam cannot be obtained. If it is at least 44% by weight, the water resistance will be insufficient. The heat-expandable graphite (C) used in the present invention is a conventionally known substance, and powders of natural scaly graphite, pyrolytic graphite, quiche graphite and the like are concentrated with sulfuric acid, nitric acid, inorganic acid such as selenic acid and concentrated nitric acid, A graphite intercalation compound formed by treatment with a strong oxidizing agent such as perchloric acid, perchlorate, permanganate, dichromate, hydrogen peroxide, etc., while maintaining the layered structure of carbon Is a crystalline compound.

In the present invention, the heat-expandable graphite obtained by the acid treatment as described above is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like. As the aliphatic lower amine, for example, monomethylamine, dimethylamine, trimethylamine,
Ethylamine, propylamine, butylamine and the like can be mentioned. Examples of the alkali metal compound and alkaline earth metal compound include hydroxides, oxides, carbonates, sulfates, and organic acid salts of potassium, sodium, calcium, barium, magnesium and the like. Specific examples of the heat-expandable graphite thus neutralized include, for example, “CA-60S” manufactured by Nippon Kasei Co., Ltd., and “GR” manufactured by Tosoh Corporation.
EP-EG ", GRAF GUARD2 manufactured by Tomoe Kogyo Co., Ltd.
20-50N and the like. The particle size of the thermally expandable graphite used in the present invention is preferably 20 to 200 mesh. If the particle size is smaller than 200 mesh, the degree of expansion of graphite is small, the desired refractory insulation layer cannot be obtained, and if the particle size is larger than 20 mesh, there is an effect in that the degree of swelling is large, but when kneading with the resin, Poor dispersibility and inevitable deterioration of physical properties. (C) contained in the foam type fire retardant composition
The amount of the components is from 1 to 44% by weight, preferably from 5 to 4%.
0% by weight, more preferably 5 to 30% by weight.
When the amount of the component (A) is 1% by weight or less, foaming is insufficient, and a good foam cannot be obtained. If it is at least 44% by weight, the water resistance will be insufficient. In the present invention, a plasticizer can be used as (D). This component (C)
May be added to the foamed fire-retardant composition for the purpose of improving rubber properties such as flexibility and molding fluidity, and for improving the water resistance of the sheet. As the plasticizer, a general plasticizer can be used, but a plasticizer having good compatibility with the polymer comprising the polyolefin compound unit of the component (A) is preferable. Specific examples of the plasticizer having good compatibility include, for example, polybutene, hydrogenated polybutene, liquid polybutadiene,
Hydrogenated liquid polybutadiene, poly-α-olefins, paraffinic oil, naphthenic oil, α-methylstyrene oligomer, atactic polypropylene and the like, among which, preferably, polybutene, hydrogenated polybutene containing no unsaturated bond, Hydrogenated liquid polybutadiene,
Hydrocarbon compounds such as polyalphaolefins, paraffin oils, naphthenic oils, and atactic polypropylene are preferred. Further, polybutene and poly-α-olefin are preferably used in view of the balance between water resistance and foaming characteristics.

When a plasticizer is compounded, the total amount of the components (A) and (D) contained in the foamed fire-retardant composition is 55 to 55.
It is 85% by weight, preferably 55-75% by weight, more preferably 60-70% by weight. When the total amount of the component (A) and the component (D) is 55% by weight or less, the water resistance is reduced. When the total amount is 85% by weight or more, a good foamed state cannot be realized, and a good foam cannot be obtained. . In the present invention, an inorganic filler can be used as the component (E). The component (E) used in the present invention is not particularly limited. For example, silica, diatomaceous earth, alumina, zinc oxide,
Titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide,
Basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawn knight, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, sodium silicate, potassium silicate, 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 "MOS", lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, water glass, stainless steel fiber, ho Examples include zinc acid, various magnetic powders, slag fibers, fly ash, dehydrated sludge, and low melting point glass. These may be used alone or as a mixture of two or more. Among the above-mentioned inorganic fillers, a hydrated inorganic substance has a property of dehydrating and absorbing heat when heated, and is therefore advantageous in increasing heat resistance. Specific examples include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. In addition, a metal salt or oxide of a metal belonging to Group II or Group III of the periodic table has a property of foaming during combustion to form a foamed fired product, and thus is preferable for enhancing shape retention. Specific examples include calcium carbonate and magnesium carbonate. Further, sodium silicate, potassium silicate, water glass, and the like are advantageous as components that can serve as a foaming component when the foam is formed and the shape stability of the foam. Further, as the component (E), a compound such as silicone oil which forms an inorganic polymer by burning can be exemplified.

[0023] The amount of the component (E) contained in the foam type fire-resistant composition is 40% by weight or less. (E) The amount of the component is 40
When the content is more than 10% by weight, water resistance becomes insufficient and a good foam cannot be obtained. In the present invention, a polyfunctional alcohol can be used as the component (F).
The component (F) is a component that is dehydrated by a phosphorus compound to form a carbonized film. Decomposition temperature of carbonization by heating is 200
C. or higher, preferably 300 C. or higher can be used.
Examples of such polyfunctional alcohols include polyhydric alcohols such as mono-, di-, and tripentaerythritol, polysaccharides such as starch and cellulose, and oligosaccharides such as glucose and fructose. From the viewpoint of properties, mono, di, and tripentaerythritol are particularly preferred. These may be used alone or in combination of two or more.

The amount of the component (F) contained in the foamed fire-resistant composition is not particularly limited, but is preferably 40% by weight or less. When the amount of the component (F) is 40% by weight or more, the water resistance becomes insufficient.

Further, in addition to the above components, an amino group-containing compound may be used as the component (G) in the foam type fire protection composition. The amino group-containing compound acts as a swelling agent, generates a nonflammable gas such as nitrogen or ammonia with decomposition by heating, and expands the entire composition to an appropriate size. Specific examples include, but are not limited to, dicyandiamide, melamine, guanamine, guanidine, urea, azodicarbonamine, and amino resins such as melamine resin, guanamine resin, and urea resin. These may be used alone or in combination of two or more. The amount of the component (G) contained in the foamed fire-resistant composition is not particularly limited, but may be 40% by weight.
The following is preferred. When the amount of the component (G) is 40% by weight or more, the strength of the formed carbonized carbon film becomes insufficient.

In the present invention, (A), (B), (C)
At least one component of (D), (E), (F), and (G) may be added to the components, but (D), (E),
Four components (F) and (G) may be added in combination.

(A), (B), (C), (D), (E)
The preferable compounding amounts of the components are as described above, but the most preferable compounding amounts are 30 to 100 parts by weight of the component (B), 5 to 200 parts by weight of the component (C), and 100 to 100 parts by weight of the component (A). D) 10 to 200 parts by weight, component (E) 0 to 1
00 parts by weight, component (F) 0 to 80, component (G) 0 to 50
It is.

In addition to the above components, the composition of the present invention may further comprise a plasticizer, a reinforcing agent, a filler, and a hindered phenol or hindered amine, if necessary, in addition to the above-mentioned components. An antioxidant, an ultraviolet absorber, a light stabilizer, a pigment, a surfactant, a tackifier and the like can be appropriately compounded.

The method for preparing the foam type fire-retardant composition of the present invention is not particularly limited. For example, the above components are blended and kneaded at room temperature or under heating using a mixer, roll, kneader, extruder or the like. Or, an ordinary method such as mixing the components after dissolving the components in an appropriate amount of a solvent can be employed.
The obtained foam type fire retardant composition is subjected to injection molding, extrusion molding,
It can be molded by a molding method usually used for thermoplastic resins such as calender molding.

The use of the foamed fire-resistant composition of the present invention is not particularly limited.
Attached or laminated to ceilings, walls, columns, beams, doors, etc., forms a heat-insulating foamed carbon layer when exposed to flames,
It can be used to prevent outflow of gas and the like generated by flame and combustion to the outside. Also, by attaching or laminating a fire-resistant ceiling material, especially on the underside of the ceiling, a heat-insulating foamed carbon layer is formed when the ceiling material is exposed to a flame during a fire, and the heat from the fire is transmitted to the beams. And can be used to prevent a decrease in strength of the beam due to heat. With such use, the fire-resistant coating on the beam can be eliminated, and the workability and workability can be significantly improved. In addition, it can also be used as a foam sheet, a foam gasket, and a molded article. Specifically, there is a usage method in which a fire or smoke can be prevented from penetrating at the time of a fire by setting a sheet or attaching a gasket to a gap between the upper, lower, left and right sides of a fire door. In addition, the air conditioner and ventilation ducts are usually installed so that they do not hinder their functions at the outlets and air intakes.In the event of a fire, they expand due to heat, block the air outlets and air intakes, and through such equipment, There is also a method of use in which smoke can be prevented from spreading and spreading.As a method of fixing the molded article to a fireproof object when the molded article is used for the above purpose, a general-purpose method is used. However, it may be fixed by a physical method such as a nail or a screw, or a chemical method such as an adhesive or an adhesive may be used. Further, the molded article may be given tackiness in advance, or an adhesive and / or pressure-sensitive adhesive layer may be laminated in advance.

[0031]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Prior to the examples, various measurement methods and evaluation methods will be described.

(Expansion property test) A molded product of 10 × 10 × 2 mm was put in a crucible, and heated by a gas burner with a flame that reached a temperature of about 600 ° C. 3 minutes after the bottom of the crucible, and the expansion ratio was heated. It was determined as the ratio of the thickness of the carbonized sheet after foaming / the thickness before heat foaming.

(Water Resistance Test) A sheet of 10 × 10 × 2 mm was immersed in warm water of 50 ° C. for 2 weeks. The foamed state of the sheet was heated and observed in the same manner as in the foaming property test. The magnification retention was defined as expansion ratio after immersion / expansion ratio before immersion × 100 (%). The external appearance was evaluated as 良好 when the surface did not have cracks, cracks or discoloration after immersion in warm water, and evaluated as × when the surface had cracks, cracks or discoloration. The shape retention of the foamed layer was evaluated as good when the shape after foaming in the foaming property test and the shape after foaming in the water resistance test were good, and poor when the shape was not the same.

(Example 1) The inside of a polymerization vessel of a 2 L separable flask was purged with nitrogen, and then n-hexane (dried with molecular sieves) 480 using a syringe.
mL and butyl chloride (dried with molecular sieves) 690 mL, p-dicumyl chloride) 0.6
47 g (2.8 mmol) were added. The polymerization vessel is -70
After cooling in a dry ice / methanol bath at a temperature of 1.2 ° C., 1.22 g of dimethylacetamide (14.0 mmol
l) was added. Next, 232 mL of isobutylene monomer
A Teflon liquid sending tube was connected to a pressure-resistant glass liquefaction sampling tube equipped with a three-way cock containing (2872 mmol), and an isobutylene monomer was sent into the polymerization vessel by nitrogen pressure. Further, 8.7 mL of titanium tetrachloride (79.1 m
mol) was added to initiate polymerization. After stirring at the same temperature for 1 hour from the start of the polymerization, about 1 mL of the polymerization solution was withdrawn from the polymerization solution for sampling. Subsequently, the styrene monomer 7 previously cooled to −70 ° C.
A mixed solution of 7.9 g (748 mmol), 14 mL of n-hexane and 20 mL of butyl chloride was added to the polymerization vessel. 10 minutes after adding the mixed solution, about 200 m
The reaction was terminated by adding L of methanol.

After the solvent and the like were distilled off from the reaction solution, it was dissolved in toluene and washed twice with water. Further, a toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. The molecular weight of the obtained polymer was measured by gel permeation chromatography (GPC). The Mw of the isobutylene polymer before the addition of styrene was 65,000, Mw / Mn was 1.2, and the Mw of the block copolymer after the styrene polymerization was 95,000.
A block copolymer having Mw / Mn of 1.6 was obtained. 100 parts by weight of the obtained styrene-isobutylene-styrene block copolymer, 30 parts by weight of ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.), and heat-expandable graphite (GRAF GUARD220-50N manufactured by Tomoe Kogyo Co., Ltd.) After melt-kneading 15 parts by weight at 170 ° C., 2 mm at 170 ° C.
It was press-molded to a thickness. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results. Example 2 100 parts by weight of the styrene-isobutylene-styrene block copolymer obtained in Example 1 and ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.)
50 parts by weight, heat-expandable graphite (GRAF GUARD2 manufactured by Tomoe Industries Co., Ltd.)
20-50N) 10 parts by weight, polybutene (Idemitsu Petrochemical 300
H) After melt-kneading 30 parts by weight at 170 ° C., 1
It was press-formed at 70 ° C. to a thickness of 2 mm. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results. Example 3 100 parts by weight of the styrene-isobutylene-styrene block copolymer obtained in Example 1 and ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.)
40 parts by weight, thermal expansive graphite (GRAF GUARD2 manufactured by Tomoe Kogyo Co., Ltd.)
20-50N) 15 parts by weight, 10 parts by weight of pentaerythritol as polyhydric alcohol, 5 parts by weight of melamine, 30 parts by weight of polybutene (300H manufactured by Idemitsu Kagaku) are melt-kneaded at 170 ° C., and then press-molded at 170 ° C. to a thickness of 2 mm. did. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results. (Example 4) 100 parts by weight of LLDPE (manufactured by Showa Denko KK, Shorex A106L), 50 parts by weight of ammonium polyphosphate (Sumisafe PM, manufactured by Sumitomo Chemical Co., Ltd.), and heat-expandable graphite (Tome Industry Co., Ltd.) GRAF GUARD220-50N)
30 parts by weight of polybutene (300H manufactured by Idemitsu Petrochemical) and 30 parts by weight of aluminum hydroxide (Heidilite H-34HL manufactured by Showa Denko KK) are melt-kneaded at 170 ° C, and then pressed at 170 ° C to a thickness of 2 mm. Molded. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results. (Example 5) Butyl rubber (Butyl 065 manufactured by Exxon)
100 parts by weight, 50 parts by weight of ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.), thermally expandable graphite
20 parts by weight (GRAF GUARD220-50N, Tomoe Kogyo Co., Ltd.), 120 parts by weight polybutene (300H, Idemitsu Petrochemical), 20 parts by weight pentaerythritol as polyhydric alcohol, calcium carbonate (Ryton A, Bihoku Powder Chemical Co., Ltd.) After melt-kneading 20 parts by weight at 170 ° C., 2 mm
It was press-molded to a thickness. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results. (Comparative Example 1) Modified silicone-based sealing agent (100 parts by weight of MS polymer manufactured by Kanegafuchi Chemical Industry Co., Ltd.), and dioctyl phthalate (DOP) as a plasticizer was added to 50 parts by weight.
Parts by weight, 100 parts by weight of ammonium polyphosphate, 15 parts by weight of thermally expandable graphite (GRAF GUARD220-50N manufactured by Tomoe Kogyo KK), and 40 of pentaerythritol as a polyhydric alcohol
After adding 15 parts by weight of dicyandiamide as an amino group-containing compound and stirring at room temperature, the mixture was further kneaded well with three rolls to form a paste. To this composition, 3 parts by weight of tin octylate as a curing catalyst and 0.75 parts by weight of laurylamine as a curing aid were added and stirred. A sheet having a thickness of 2 mm was prepared using the composition thus obtained, and then cured at 23 ° C. for 1 week and further at 50 ° C. for 1 week. Further, the above composition was poured into a mold of 10 × 20 × 2 mm, and this was cured at 23 ° C. for 1 week and further at 50 ° C. for 1 week. The molded product was subjected to a foaming property test and a water resistance test. Table 2 shows the results. Comparative Example 2 100 parts by weight of the styrene-isobutylene-styrene block copolymer obtained in Example 1 and ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.)
100 parts by weight, heat-expandable graphite (Toma Kogyo Co., Ltd. GRAF GUAR
D220-50N) 30 parts by weight were melt-kneaded at 170 ° C., and then press-molded at 170 ° C. to a thickness of 2 mm. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results. (Comparative Example 3) 100 parts by weight of LLDPE (Showa Denko Co., Ltd., Shorex A106L), 50 parts by weight of ammonium polyphosphate (Sumisafe PM, manufactured by Sumitomo Chemical Co., Ltd.), and heat-expandable graphite (Tome Kogyo Co., Ltd.) GRAF GUARD220-50N)
After melt-kneading 30 parts by weight and 150 parts by weight of aluminum hydroxide (Heidilite H-34HL manufactured by Showa Denko KK) at 170 ° C, the mixture was press-formed at 170 ° C to a thickness of 2 mm.
The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results. (Comparative Example 4) IIR (Butyl 065 manufactured by JSR) 100
Parts by weight, 200 parts by weight of ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.), 120 parts by weight of polybutene (300H manufactured by Idemitsu Kaika), 8 parts by weight of tackifying resin (Alcon P-125 manufactured by Arakawa Chemical Co., Ltd.), water 100 parts by weight of aluminum oxide, expandable graphite (GRAFGUA manufactured by Tomoe Industries)
(RD220-50N) 60 parts by weight and a composition comprising 200 parts by weight of calcium carbonate (Ryton A manufactured by Bihoku Powder Chemical Co., Ltd.) were melt-kneaded at 170 ° C, and then 2 parts at 170 ° C.
It was press-molded to a thickness of mm. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded article were evaluated. Table 2 shows the results.

As shown in Table 2, it was confirmed that the compositions of Examples 1 to 5 formed an incombustible foamed carbonized layer having a sufficient effect on fire protection and heat insulation, and were excellent in water resistance. Furthermore,
Compared with the composition of the modified silicone-based sealing agent of Comparative Example 1, it was revealed that the molding processability was excellent. In addition, the compositions of Comparative Examples 2 to 4 were immersed in warm water,
When the foaming was evaluated, the shape of the foam became indefinite and the expansion ratio could not be measured.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

As described above, the fire-retardant foamed resin composition of the present invention has excellent moldability and can easily form a large-area sheet. Furthermore, it has excellent water resistance. Such a composition is excellent because it can be widely applied to places where fire protection and fire resistance are required in general buildings.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/16 C08K 5/16 5/49 5/49 C08L 23/00 C08L 23/00 23/20 23 / 20 23/22 23/22 53/02 53/02 F term (reference) 4J002 AA01W AC00W AC01W AC03W AC06W AC07W AC09W BB00X BB01W BB15W BB17X BB18W BP01W CP03W DA027 DE068 DE088 DE108 DE128 DE138 DE148 DE208 DG048 FD006 DJ0 018 006 FD02X FD136 FD137 FD209 GT00

Claims (10)

[Claims] 1. A foamable fire-retardant composition comprising (A) a thermoplastic resin and / or a rubber-based material, (B) a phosphorus compound and (C) thermally expandable graphite, wherein the composition comprises A foamed fire-resistant resin composition containing (A) in an amount of 50 to 85% by weight. 2. The foam type fire-retardant composition further comprising (D) a plasticizer, wherein the composition contains 55 to 85% by weight in total of (A) and (D). The foam-type fire-retardant composition according to the above. 3. The foam-type fire-retardant composition according to claim 1, further comprising (E) an inorganic filler. 4. The foam type fire-retardant composition according to claim 1, further comprising (F) a polyfunctional alcohol. 5. The foam-type fire-retardant composition according to claim 1, further comprising (G) an amino group-containing compound. 6. The method according to claim 1, wherein (A) the thermoplastic resin and / or the rubber-based material is a polymer having at least one polymer chain obtained by polymerizing a monomer composed of an olefin-based compound. The foam-type fire-retardant composition according to the above. 7. The foam type fire retardant composition according to claim 6, wherein the thermoplastic resin (A) is a block copolymer comprising an aromatic vinyl compound unit and an olefin compound unit. 8. The foam type fire-retardant composition according to claim 6, wherein the olefin-based compound unit in the block copolymer (A) is a compound unit mainly composed of isobutylene. 9. The foam-type fire-retardant composition according to claim 6, wherein the rubber material (A) is butyl rubber. 10. The foam-type fire-retardant composition according to claim 2, wherein (D) the plasticizer is polybutene and / or poly-α-olefin.