JP2000336238A - Foamable fireproof composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition from which a wide sheet can be easily formed because of excellent formability and which expands and foams when heated to form a carbonized layer by using as the constituents a polyphosphoric salt compound and a block copolymer consisting of aromatic vinyl compound units and olefin compound units. SOLUTION: It is desirable that the olefin compound units of the block copolymer are units of a compound comprising mainly isobutylene from the viewpoint of enhancing the water resistance of the copolymer, The polyphosphoric salt compound preferably comprises an ammonia or amine salt of polyphosphoric acid, and it is blended preferably in an amount of 10-400 pts.wt. based on 100 pts.wt. block copolymer. It is desirable to incorporate a polyfunctional alcohol (e.g. pentaerithritol), preferably in an amount of 10-200 pts.wt., and/or an aminated compound (e,g, melamine), preferably in an amount of 5-100 pts,wt, into the composition. The composition forms a carbonized layer which prevents a combustible material from firing and prevents a gas from flowing out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foam-type fire-retardant composition, and more particularly to a foamed fire-retardant composition which is used by sticking it around beams, ceilings, and openings of doors of general buildings, and when exposed to a flame, forms carbonized foam. Form a layer to prevent fires such as wood and other combustible materials,
The present invention relates to a foam type fire-retardant composition having an effect of preventing outflow of smoke, flame, gas generated by combustion, and the like to the outside.

[0002]

2. Description of the Related Art Conventionally, a beam or the like of a building has been coated with a fire-resistant material in order to enhance the fire protection performance of the building. The current fire-resistant coating is sprayed with a semi-moist type fire-resistant material (rock wool or the like). Is the mainstream. However, according to this method, the material is liable to be scattered at the time of work, and curing is required to prevent the material from being scattered. 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, these parts are not suitable for use in areas having mobility around openings such as doors, because these fireproof and fireproof sheets have poor elasticity and extremely poor displacement followability. On the other hand, Japanese Unexamined Patent Publication Nos. Hei 3-31379 and Hei 9-53075 disclose the use of ammonium polyphosphate, polyhydric alcohols, amino group-containing compounds and the like in sealing materials used for building materials. There has been proposed a foam type fire-resistant sealant composition containing: These foam-type fire-resistant sealant compositions form a non-combustible foamed carbonized layer when exposed to a flame, thereby preventing flammable materials such as wood from being fire-protected or from emitting smoke, flame, and gas generated by combustion. Can be prevented. Further, Japanese Patent Application Laid-Open No. Hei 10-18433 proposes a fire-resistant coated sheet using the foam type fire-resistant sealant composition.

[0003] However, the sheet made of these sealant compositions has a low strength as a rubber, and is obtained by pouring and curing a liquid composition into a mold. Was not suitable.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned problems in the prior art, an object of the present invention is to form a carbonized layer which is expanded and foamed by heating to prevent combustibles from being fired, and to reduce smoke and smoke.
An object of the present invention is to provide a foam-type fire-retardant composition using a block copolymer, which has an effect of preventing outflow of gas and the like generated by flame and combustion to the outside.

[0005]

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, by applying a block copolymer, a foaming mold excellent in stretchability, strength and workability has been obtained. A fire retardant composition has been obtained. That is, the present invention is a foamable fire-retardant composition containing (A) a block copolymer comprising an aromatic vinyl-based compound unit and an olefin-based compound unit and (B) a polyphosphate compound.
In the present invention, the foamable fire-retardant composition may further contain at least one of (C) a polyfunctional alcohol and (D) an amino group-containing compound.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the component (A) of the present invention, a block copolymer comprising an aromatic vinyl compound unit and an olefin compound unit is used.

The aromatic vinyl compounds include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene and p-methylstyrene.
Examples include methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, and indene. Among the above compounds, styrene, α-methylstyrene, p-methylstyrene and indene are preferred in view of the balance between cost, physical properties and productivity, and two or more of them may be combined.

The olefinic compound unit includes olefinic compounds having 1 to 6 carbon atoms such as ethylene, propylene, 1-butylene, isobutylene, butadiene and isoprene, and two or more of them may be combined.

Further, specific examples of the olefin-based compound polymer obtained from the above compound include polybutadiene, polyisoprene, and a hydrogenated product of polyethylene.
Butylene, polyethylene propylene, and polyisobutylene.

In particular, the polyphosphate compound as the component (B) of the present invention has high water absorption, and there is a concern that the water absorption may lower the foaming performance of the composition of the present invention. Therefore, as the olefin-based compound polymer, a polymer mainly composed of isobutylene having low water vapor permeability is particularly preferable. In order to increase the water resistance of the block copolymer, it is desirable that the isobutylene-based compound be 50% by weight or more in the olefin-based compound.

The block copolymer used in the present invention comprises:
As long as it has a unit mainly composed of an aromatic vinyl compound and a unit mainly composed of an olefinic compound, those having any structure can be used,
From the balance of physical properties and simplicity of synthesis, a triblock having a structure of (unit mainly composed of aromatic vinyl compound-unit mainly composed of olefinic compound-unit mainly composed of aromatic vinyl compound), A diblock having a structure of (unit mainly composed of olefin-based compound-unit mainly composed of aromatic vinyl-based compound) or a mixture thereof can be used.

The ratio of the unit mainly composed of an olefinic compound to the unit mainly composed of an aromatic vinyl compound in the block copolymer is not particularly limited. 95-
20 parts by weight and preferably 5 to 80 parts by weight of a monomer mainly composed of an aromatic vinyl compound, and more preferably 90 to 60 parts by weight of a monomer mainly composed of an olefin compound and mainly composed of an aromatic vinyl compound Preferred is 10 to 40 parts by weight of monomer.

The number average molecular weight of the block copolymer is not particularly limited, but the number average molecular weight of the block copolymer is 3
0000 to 500,000 is preferred, and 50,000
0 to 400,000 is particularly preferred. Number average molecular weight is 3
If it is less than 000, mechanical properties and the like are not sufficiently exhibited, and if it exceeds 500,000, the moldability and the like are greatly reduced.

A plasticizer may be added to the component (A) for the purpose of improving rubber properties such as flexibility and molding fluidity.
Although generally used plasticizers can be used, those having good compatibility with the polymer comprising the polyolefin compound unit of the component (A) are preferable. Specific examples of the plasticizer having good compatibility include, for example, polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffinic oil, naphthenic oil, α-methylstyrene oligomer, atactic polypropylene, and the like. Among them, hydrocarbon compounds such as hydrogenated polybutene containing no unsaturated bond, hydrogenated liquid polybutadiene, paraffinic oil, naphthenic oil and atactic polypropylene are preferred.

When a plasticizer is added, the amount is preferably 10 to 400 parts by weight based on 100 parts by weight of the total of the component (A) and the plasticizer.

As the component (B) of the present invention, a polyphosphate compound is used. This polyphosphate compound acts as a dehydration catalyst for organic substances in a heated environment,
It has a function of forming a nonflammable inorganic phosphoric acid film itself. The polyphosphate compound is not particularly limited as long as it is a salt of polyphosphoric acid, but is preferably a salt of polyphosphoric acid with ammonia or an organic base, more preferably a salt of polyphosphoric acid with ammonia or an amine, particularly preferably polyphosphoric acid. Ammonium is preferred. Examples of the amine compound forming the salt include methylamine and ethylamine. When a polyphosphoric acid salt with ammonia or an amine reaches a decomposition temperature by heating, condensed phosphoric acid is 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, ammonia gas or the like generated at this time acts as a foaming agent and expands the entire composition. The salt of polyphosphoric acid with ammonia or amine used in the present invention has a phosphorus content of 15% by weight, a nitrogen content of 14% by weight, a decomposition temperature of 200 ° C. or more, and has a low hygroscopicity from the viewpoint of easy handling. Things are suitable. Such a salt of polyphosphoric acid with ammonia or amine is not particularly limited. For example, an insolubilized high-molecular phosphorus compound made of Sumitomo Chemical Co., Ltd. made of ammonium polyphosphate (trade name “Sumisafe P
M ").

The amount of the component (B) is not particularly limited, but is preferably 10 to 400 parts by weight based on 100 parts by weight of the block copolymer as the component (A). If the compounding amount of the component (B) is less than 10 parts by weight, it is impossible to effectively carbonize and foam the entire composition. Conversely, if the compounding amount of the component (B) exceeds 400 parts by weight. It is not preferable because the viscosity of the compound tends to increase and the moldability tends to decrease.

In the present invention, a polyfunctional alcohol may be used as the component (C) in addition to the components (A) and (B). The polyfunctional alcohol expands by heating, and forms a foamed carbonized film by carbonization in the presence of a polyphosphate compound as a dehydration catalyst. Those having a decomposition temperature of 200 ° C. or higher, preferably 300 ° C. or higher, which is carbonized by heating can be used. Examples of such polyfunctional alcohols include, but are not limited to, polyhydric alcohols such as mono, di, and tripentaerythritol, polysaccharides such as starch and cellulose, and oligosaccharides such as glucose and fructose. Not something. These may be used alone or in combination of two or more.

The amount of the component (C) is not particularly limited, but 10 to 200 parts by weight or a plasticizer is added to 100 parts by weight of the block copolymer as the component (A). In this case, the total of the component (A) and the plasticizer is 10
The amount is preferably 10 to 200 parts by weight with respect to 0 parts by weight. If the amount of component (C) is less than 10 parts by weight, the expansion will be insufficient, and if the amount of component (C) exceeds 200 parts by weight, the formation of the foamed carbonized film will be insufficient.

Further, in the present invention, an amino group-containing compound may be used as the component (D) in addition to the components (A), (B) and (C). The amino group-containing compound acts as a swelling agent, generates an incombustible gas such as nitrogen or ammonia with decomposition by heating, and has the effect of expanding the entire composition to an appropriate size.

Specifically, dicyandiamide, melamine,
Examples thereof include, but are not limited to, guanamine, guanidine, urea, azodicarbonamine, melamine resin, amino resin such as guanamine resin and urea resin. These may be used alone or in combination of two or more.

The amount of the component (D) is not particularly limited, but is 5 to 100 parts by weight, or a plasticizer, based on 100 parts by weight of the block copolymer as the component (A). In this case, the total of the component (A) and the plasticizer is 100
It is preferably 5 to 100 parts by weight based on parts by weight. If the amount of component (D) is less than 5 parts by weight, the expansion will be insufficient, and if the amount of component (D) exceeds 100 parts by weight, the strength of the foamed carbonized film will be insufficient. It tends to be.

In the present invention, it is preferable that at least one component of (C) and (D) is added to both components (A) and (B), but the two components (C) and (D) are used in combination. Most preferably, it is added as an additive. In addition, the composition of the present invention, in addition to the above components, as required, in addition to the above components, as well as a plasticizer, a reinforcing agent, and a filler, as well as a hindered phenol-based or hindered amine-based antioxidant, according to the properties required for each application. Agents, ultraviolet absorbers, light stabilizers, pigments, surfactants, tackifiers 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-mentioned 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 foamed fire-retardant composition thus obtained can be molded by a molding method usually used for thermoplastic resins, such as injection molding, extrusion molding, and calendar molding.

Further, the foam type fire-retardant composition of the present invention 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.

[0026]

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.

(Rubber physical property test) A No. 3 dumbbell was punched out of a sheet having a thickness of 2 mm according to JIS K6301, and a tensile test was performed at a tensile speed of 500 mm / min.

(Expansion property test) A molded product of 10 × 20 × 10 mm was heated with a flame of about 900 ° C. by a gas burner.
The foaming state was observed.

(Water resistance test) Using a sample similar to that used for observing the above foaming characteristics, warm water at 50 ° C. was used.
After immersion for a week, the foaming state was observed in a wet state.

(Example 1) Styrene-butadiene-styrene block copolymer (KRAT manufactured by Shell Japan K.K.)
ON D-1102) 150 parts by weight, ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.) 100 parts by weight,
40 parts by weight of pentaerythritol as a polyhydric alcohol and 15 parts by weight of melamine as an amino group-containing compound
After melt-kneading at 70 ° C., press molding was performed at 170 ° C. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded product were evaluated. Table 1 shows the results.

Example 2 Styrene-ethylene / butylene-styrene block copolymer (Shell Japan Co., Ltd.)
150 parts by weight of KRATON G1650, 100 parts by weight of ammonium polyphosphate (Sumisafe PM, manufactured by Sumitomo Chemical Co., Ltd.), 40 parts by weight of pentaerythritol as a polyhydric alcohol, and 15 parts by weight of melamine as an amino group-containing compound at 170 ° C. After melt-kneading, press molding was performed at 170 ° C. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded product were evaluated. Table 1 shows the results.

Example 3 150 parts by weight of styrene-ethylene-propylene-styrene block copolymer (Septon 4033 manufactured by Kuraray Co., Ltd.) and 100 parts by weight of ammonium polyphosphate (Sumisafe PM manufactured by Sumitomo Chemical Co., Ltd.) ,
40 parts by weight of pentaerythritol as a polyhydric alcohol and 15 parts by weight of melamine as an amino group-containing compound
After melt-kneading at 70 ° C., press molding was performed at 170 ° C. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded product were evaluated. Table 1 shows the results.

(Example 4) The inside of a polymerization vessel of a 500 mL separable flask was purged with nitrogen, and then, using a syringe,
n-hexane (dried with molecular sieves)
120 mL and methylene chloride (dried with molecular sieves) 80 mL, p-dicumyl chloride)
0.0876 g (0.38 mmol) was added. After cooling the polymerization vessel in a dry ice / methanol bath at -70 ° C, 0.036 g of 2-methylpyridine (0.
39 mmol) was added. Next, isobutylene monomer 3
A Teflon feed tube was connected to a pressure-resistant glass liquefaction sampling tube equipped with a three-way cock containing 3.9 mL (419.9 mmol), and the isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 1.50 mL of titanium tetrachloride
(13.7 mmol) 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, a mixed solution of 12.15 g (116.7 mmol) of styrene monomer, 12 mL of n-hexane, and 8 mL of methylene chloride, which had been cooled to −70 ° C. in advance, was added to the polymerization vessel. After adding the mixed solution, 10
After one minute, about 10 mL of methanol was added to terminate the reaction.

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 Mn of the isobutylene polymer before styrene addition was 70,000, Mw / Mn was 1.16, and the Mn of the block copolymer after styrene polymerization was 101,00.
0, and a block copolymer having Mw / Mn of 1.40 was obtained.

150 parts by weight of the obtained styrene-isobutylene-styrene block copolymer, 100 parts by weight of ammonium polyphosphate (Sumisafe PM, manufactured by Sumitomo Chemical Co., Ltd.), 40 parts by weight of pentaerythritol as a polyhydric alcohol, containing an amino group After melt-kneading 15 parts by weight of melamine as a compound at 170 ° C., it was press-molded at 170 ° C. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded product were evaluated. Table 1 shows the results.

[0036]

[Table 1]

(Comparative Example) A modified silicone-based sealing agent (100 parts by weight of MS polymer manufactured by Kaneka Chemical Industry Co., Ltd.) was used, and dioctyl phthalate (DO) was used as a plasticizer.
50 parts by weight of P), 100 parts by weight of ammonium polyphosphate, and 4 parts of pentaerythritol as a polyhydric alcohol.
0 parts by weight and 15 parts by weight of dicyandiamide as an amino group-containing compound were added, and the mixture was stirred at room temperature. 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. Using the composition thus obtained, a sheet having a thickness of 2 mm was prepared, and then at 23 ° C. for 1 week and further at 50 ° C. for 1 week.
Cured for a week. From the obtained cured product sheet, JISK6
A No. 3 dumbbell was punched out according to No. 301, and a tensile test was performed at a tensile speed of 500 mm / min. Furthermore, 10 ×
The above composition was poured into a 20 × 10 mm mold,
Cured for 1 week at 50 ° C and further for 1 week at 50 ° C. The molded product was subjected to a foaming property test and a water resistance test. Table 1 shows the results.

As shown in Table 1, it was confirmed that the compositions of Examples 1 to 4 formed a non-combustible foamed carbonized layer having a sufficient effect on fire protection and heat insulation, although the expansion ratio was lower than that of the comparative example. did it. Furthermore, it became clear that the modified silicone sealant composition of the comparative example was superior in tensile strength as rubber and excellent in moldability.
Further, in Example 4, which is composed of a styrene-isobutylene-styrene block copolymer, it is clear that the composition has a small reduction in the expansion ratio after the water resistance test and is excellent in water resistance.

[0039]

As described above, since the foamable curable composition of the present invention is rich in elasticity and excellent in rubber properties, it can be used in places where displacement followability is required such as door openings. It is also suitable, and is excellent in formability, and facilitates the formation of a large-area sheet. Such a composition is excellent because it can be widely applied to places where fire protection and fire resistance are required in general buildings.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/04 C09K 21/04 21/12 21/12 21/14 21/14 (72) Inventor Ryuji Fukuda 302, Kita-Ochiai, Suma-ku, Kobe-shi, Hyogo Prefecture (72) Inventor Tomoki Nishiro 1-4, Cha-enba-cho, Akashi-shi, Hyogo (72) Inventor Taizo Aoyama 4-13-10, Nishihata, Takasago-shi, Hyogo F-term (reference) 4F074 AA16B AA32B AC31 AD04 AD13 AG17 AG20 BA08 BA84 BB08 CA22 CC04Y DA50 DA59 4H028 AA07 AA24 AA42 AB03 AB04 BA03 BA06 4J002 AB012 AB042 BP011 CC163 CC183 CC193 DH056 EC037 FD FD 018 018 FD 018 FD 018 FD 198

Claims (4)

[Claims] 1. A foam type fire-retardant composition comprising (A) a block copolymer comprising an aromatic vinyl compound unit and an olefin compound unit and (B) a polyphosphate compound. 2. The foam-type fire-retardant composition according to claim 1, further comprising (C) a polyfunctional alcohol. 3. The foam type fire-retardant composition according to claim 1, further comprising (D) an amino group-containing compound. 4. The foam-type fire-retardant composition according to claim 1, wherein the olefinic compound unit in the block copolymer (A) is a compound unit mainly composed of isobutylene.