JP2002322374A - Foamed fire-retardant composition with excellent fire resistance - Google Patents

Abstract

[PROBLEMS] To prevent combustibles by forming a carbonized layer that is excellent in formability into a sheet, expands and expands by heating, and has excellent fire resistance and heat insulation properties. The present invention provides a fire-resistant composition having excellent water resistance and / or moisture resistance. (A) a thermoplastic resin, (B) a phosphorus compound,
(C) a foamed fire-retardant composition comprising a polyfunctional alcohol, (D) an inorganic fiber material, and (E) an inorganic filler, wherein the (D) inorganic fiber material is glass fiber,
(E) The inorganic filler is calcium carbonate, magnesium carbonate, fused silica, crystalline silica, diatomaceous earth, clay, talc, mica, kaolin, titanium oxide, zinc oxide, aluminum oxide, carbon black, bentonite, aluminum hydroxide, hydroxide It is preferably at least one selected from the group consisting of magnesium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamed fire-retardant composition having excellent sheet formability, water resistance, and particularly excellent fire and heat insulation properties.

[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. Further, as a means for solving these problems, a plate-like fireproof / fireproof board made mainly of calcium silicate, gypsum or the like may be used. However, since these fireproof / fireproof boards are brittle, they often break, such as cracks or cracks, when transported from the board making place to the construction place, and cutting at the construction site is not easy. On the other hand, various fireproof / fireproof sheets made of an inorganic compound such as ceramic and a nonwoven fabric have been proposed. However, such a fire-resistant and fire-resistant sheet is not suitable for use on a portion having mobility around an opening, such as a door, because the sheet has poor elasticity and remarkably poor displacement followability.

On the other hand, a fire-resistant rubber composition which can be processed into a sheet and has elasticity has been proposed. JP-A-10-1
95250 proposes a fire-resistant rubber composition containing a rubber-based material, a phosphorus compound, a hydrocarbon compound having a hydroxyl group in a molecule, and an inorganic filler. The fire resistance of such a refractory composition is such that the phosphorus compound acts as a catalyst for dehydrating organic substances due to heat or flame at the time of fire, and in particular, dehydrates a hydrocarbon compound having a hydroxyl group to foam and carbonize it. By acting as a material, a strong foamed carbonized layer is formed. The thermal insulation and fire resistance of the foamed carbonized layer formed from such a composition largely depends on the expansion / expansion ratio. However, although the carbonized layer formed from this composition is strong, it has insufficient foaming / expansion ratio, and thus has a problem of poor heat insulation and fire resistance.
In a high temperature range such as 0 ° C. or higher, high fire resistance cannot be exhibited.

Further, phosphorus compounds and hydrocarbon compounds having a hydroxyl group in a molecule are liable to bleed out when they are blended with rubber or thermoplastic resin. Therefore, when this composition is formed into a sheet, the surface of a calender roll is required. There was a problem in the moldability, such as sticking to the surface of the extruder and the appearance of blemishes on the die of the extruder. In addition, since phosphorus compounds and hydrocarbon compounds having a hydroxyl group in the molecule have significantly reduced fire resistance due to moisture and water in the air, foam-type fire-resistant sheets made of this composition that cause bleed-out have long been used. Over a long period of time, and there was also a problem in terms of water resistance and / or moisture resistance.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned problems in the prior art, it is an object of the present invention to provide an excellent sheet formability, shape retention (strength) expanded and foamed by heating, and fire and heat insulation. An object of the present invention is to provide a fire-retardant composition which is excellent in water resistance and / or moisture resistance by forming a carbonized (ashed) layer having excellent heat resistance to combustible substances.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, added a phosphorus compound, a polyfunctional alcohol, an inorganic fiber material, and an inorganic filler to a thermoplastic resin. By doing so, it is excellent in formability to form a sheet, forms a carbonized layer having high fire and heat insulation properties expanded and foamed by heating and / or flame, and has excellent water resistance and / or moisture resistance, elasticity, and strength. Thus, a foam-type fire-retardant composition having excellent heat resistance was obtained.

That is, the present invention provides (A) a thermoplastic resin,
A foamable fire-retardant composition comprising (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic fiber material, and (E) an inorganic filler. The composition further comprises (F) ) It may contain a plasticizer and may further contain an amino group-containing compound (G). Further, the total content of (D) the inorganic fiber material and (E) the inorganic filler (D + E)
Is 10 to 2 parts per 100 parts by weight of the thermoplastic resin (A).
And the weight ratio (D / E) of (D) inorganic fiber material to (E) inorganic filler is 0.05 to 2 parts by weight.
It is preferably added so as to be 0.

(A) The thermoplastic resin is preferably a thermoplastic elastomer, and the thermoplastic elastomer is preferably a block copolymer, and the block copolymer is made of an aromatic vinyl compound. What consists of a block and a block which consists of an olefinic compound is more preferred. Further, the block composed of an olefin compound in the block copolymer is preferably a block mainly composed of isobutylene. (D) As the inorganic fiber material, a material having a melting point of 1200 ° C. or less is preferable, and among them, glass fiber is preferable. (E) As inorganic fillers, calcium carbonate, magnesium carbonate, fused silica, crystalline silica, diatomaceous earth, clay,
It is preferably at least one selected from the group consisting of talc, mica, kaolin, titanium oxide, zinc oxide, aluminum oxide, carbon black, bentonite, aluminum hydroxide, and magnesium hydroxide, and is a non-sinterable filler. Is more preferable, and among them, silica is further preferable. (F) The plasticizer is preferably at least one selected from poly-α-olefins and polybutenes.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The foam type fire-retardant composition of the present invention comprises:
It contains (A) a thermoplastic resin, (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic fiber material, and (E) an inorganic filler. Although the mechanism of foaming and carbonization by heating and / or flame of the product is unclear, it involves chemical decomposition and / or reaction,
It is capable of forming a carbonized (ashed) layer having a stable and high heat insulating property.

(A) The thermoplastic resin is not particularly limited, and for example, at least one selected from the group consisting of plastics, rubbers, and thermoplastic elastomers can be used. Examples of the plastics include polyolefins such as polypropylene and polyethylene, polystyrene, ABS, MBS, acryl, polyurethane, polyvinyl chloride, polyester, polyamide and the like. Examples of rubbers include polyether, polybutadiene, natural rubber, butyl rubber, chloroprene rubber, ethylene-propylene rubber, and the like.

The thermoplastic elastomers include, for example, styrene-based block copolymers composed of polystyrene blocks and polyisoprene blocks and the like, olefins composed of polyolefin components such as polypropylene and rubber components such as ethylene-propylene rubber, Polyvinyl chloride based on crystalline and non-crystalline polyvinyl chloride, urethane based block copolymer composed of polyurethane block and polyether block, polyester based block copolymer composed of polyester block and polyether block And amide-based block copolymers composed of polyamide blocks and polyether blocks. At least one of these thermoplastic resins can be used regardless of the classification of plastics, rubbers, and thermoplastic elastomers.

Among the above thermoplastic resins, a thermoplastic elastomer is preferable in view of processability, flexibility and strength, and a block copolymer is more preferable. In particular, a block composed of a block composed of an aromatic vinyl compound such as styrene and a block composed of an olefin compound is preferable. When such a block copolymer is used, the sheet is more flexible and easier to process than other thermoplastic resins, and it is easy to coat a complicated shape. The block composed of the aromatic vinyl compound refers to a block in which the aromatic vinyl compound accounts for 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more. The block composed of the olefinic compound means that the olefinic compound is 50% by weight or more, preferably 70% by weight or more,
More preferably, it refers to a block occupying 90% by weight or more.

As the aromatic vinyl compound, styrene,
α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene,
Examples include dichlorostyrene, methoxystyrene, indene and the like. Of the above compounds, styrene, α-methylstyrene, p-methylstyrene, and indene are preferred from the balance of physical properties and productivity, and two or more of them may be selected.

Examples of the olefinic compound include 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 selected. Further, specific examples of the block composed of the olefinic compound obtained from the above compound include a polybutadiene block,
Examples include polyisoprene blocks and their hydrogenated polyethylene butylene blocks, polyethylene propylene blocks, and polyisobutylene blocks. Among them, a polyisobutylene block containing a large amount of tertiary carbon necessary for forming a stable and strong carbonized layer, having a high water vapor barrier property, and hardly causing a crosslinking reaction during thermal decomposition is particularly preferable.

The polyisobutylene block refers to 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.

The number average molecular weight of the block copolymer composed of the block composed of the aromatic vinyl compound and the block composed of the olefinic compound is not particularly limited.
000 to 500,000 is preferred, and 40,000
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. The ratio of the olefin compound and the aromatic vinyl compound is not particularly limited, but from the balance of physical properties, 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 furthermore, the olefin compound 90 to 60 parts by weight and aromatic vinyl compound 1
0 to 40 parts by weight is more preferred.

(B) The phosphorus compound is not particularly limited, but red phosphorus; phosphates such as triphenyl phosphate and tricresyl phosphate; metal phosphates such as sodium phosphate and magnesium phosphate; phosphoric acid At least one selected from the group consisting of ammonium; salts or amides of phosphoric acid with an organic base such as melamine; ammonium polyphosphate; salts or amides of polyphosphate with an organic base such as melamine or the like is used. The polyphosphoric acid is not particularly limited as long as phosphoric acid is condensed, but is preferably a 2- to 5000-mer of phosphoric acid.

These phosphorus compounds (B) not only act as a catalyst for dehydrating and / or carbonizing organic substances under a heated environment, but also have a function of forming a nonflammable inorganic phosphoric acid film. Among the above phosphorus compounds, salts of phosphoric acid or polyphosphoric acid, and phosphoric acid or polyphosphoric acid amide are preferable. As the salt of phosphoric acid or polyphosphoric acid, a salt of phosphoric acid or polyphosphoric acid with ammonia or an organic base is preferable, and particularly, ammonium polyphosphate or a derivative thereof is more preferable. 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 phosphoric acid or polyphosphoric acid amide, phosphoric acid or polyphosphoric acid melamineamide is particularly preferred. When a salt or amide with phosphoric acid or ammonium polyphosphate or an 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 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 start temperature of 180 ° C. or more.

Such salts and amides with phosphoric acid or ammonium polyphosphate or amine are not particularly limited. For example, an insolubilized high-molecular phosphorus compound (trade name) manufactured by Sumitomo Chemical Co., Ltd. consisting of ammonium polyphosphate "Sumisafe PM"), coated ammonium polyphosphate (trade name "TERAGE C80") manufactured by Chisso Corporation, and the like.

The amount of the phosphorus compound (B) is not particularly limited, but is preferably from 10 to 120 parts by weight based on 100 parts by weight of the thermoplastic resin (A).
If the amount of the phosphorus compound falls below this range, it is not possible to expect that the entire composition will be effectively carbonized and foamed.
On the other hand, if the compounding amount of the phosphorus compound exceeds this range, the viscosity of the compound is increased and the moldability is undesirably reduced.

The polyfunctional alcohol (C) is dehydrated by the phosphorus compound (B) to form a carbonized film. The decomposition temperature of carbonization by heating is 180 ° C. or higher, preferably 2 ° C.
Those having a temperature of 20 ° 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. In terms of characteristics, especially things,
Di, tripentaerythritol is particularly preferred. Also,
These may be used alone or in combination of two or more.

The amount of the polyfunctional alcohol (C) is not particularly limited, but the thermoplastic resin (A) 10
The amount is preferably 5 to 90 parts by weight based on 0 parts by weight. If the amount of the polyfunctional alcohol component (C) falls below this range, the expansion will be insufficient, and conversely, (C)
If the compounding amount of the polyfunctional alcohol component exceeds this range, formation of the foamed carbon film becomes insufficient.

Most of the carbonized layer formed from the (B) phosphorus compound and the (C) polyfunctional alcohol is decomposed and gasified at about 600 ° C. Therefore, (A) a thermoplastic resin and (B) a phosphorus With a composition comprising a compound and (C) a polyfunctional alcohol, it is difficult to form a carbonized layer exhibiting fire resistance at 600 ° C. or higher. So 600 ° C
As described above, in order to maintain fire resistance, the foam type fire-retardant composition of the present invention further requires (D) an inorganic fiber material and (E) an inorganic filler. In the present invention, the inorganic fiber material (D) is a concept used separately from other inorganic fillers.

The effects of the (D) inorganic fiber material and the (E) inorganic filler in the foamable refractory composition of the present invention are considered to be roughly divided into two. One is an effect of reinforcing the heat-insulating foamed carbon layer formed from the (B) phosphorus compound and the (C) polyfunctional alcohol as an aggregate, and the other is an effect of reinforcing the carbonized foamed carbon layer of 60%
When heated to 0 ° C. or more, it remains as an ashing component and has the effect of maintaining heat insulation and fire resistance performance in a high temperature range. When only the former effect (the effect of the carbonized layer as an aggregate) is exerted, either (D) the inorganic fiber material and (E) the inorganic filler may be used alone or in combination. Although it is possible, in order to exhibit the latter effect (insulation and fire resistance at 600 ° C. or more), it is necessary to mix (D) the inorganic fiber material and (E) the inorganic filler in combination. That is,
When only (D) an inorganic fiber material is used in addition to (A) a thermoplastic resin, (B) a phosphorus compound, and (C) a polyfunctional alcohol, shrinkage, cracking, and Cracks are likely to occur, and (A) a thermoplastic resin;
When only (E) an inorganic filler is used in addition to (B) a phosphorus compound and (C) a polyfunctional alcohol, the strength of the incinerated layer is reduced at 600 ° C. or higher, and the fire resistance is increased due to the high density. Problems tend to occur.

That is, in addition to (A) a thermoplastic resin, (B) a phosphorus compound, and (C) a polyfunctional alcohol, (D)
By adding both the inorganic fiber material and the inorganic filler (E), the problem of adding (D) or (E) alone can be solved. It is possible to sufficiently exhibit fire resistance performance.

The total blending amount (D + E) of (D) the inorganic fiber material and (E) the inorganic filler is (A) 100% of the thermoplastic resin.
10 to 200 parts by weight with respect to parts by weight, and
It is preferable that the weight ratio (D / E) of (D) the inorganic fiber material to (E) the inorganic filler is 0.05 to 20. If the total amount of the (D) inorganic fiber material and the (E) inorganic filler is more than 200 parts by weight, the expansion ratio of the carbonized layer is reduced, and high fire resistance is not exhibited, and the flexibility of the composition is reduced. Is not preferred. If the total amount of (D) the inorganic fiber material and (E) the inorganic filler is less than 10 parts by weight, the density of the ashed layer becomes low when ashed at 600 ° C. or more, and a penetrating portion is formed. The problem that the contribution as a heat insulating layer is reduced is likely to occur. When the weight ratio (D / E) of the (D) inorganic fiber material and the (E) inorganic filler is less than 0.05, at 600 ° C. or more,
The strength of the ashed layer is reduced, and the fire resistance is apt to be reduced due to the high density. If it is 20 or more, problems such as shrinkage, cracking, and cracking of the ashed layer are likely to occur.

(D) The inorganic fiber material is not particularly restricted but includes, for example, rock wool, glass fiber, carbon fiber,
At least one selected from the group consisting of ceramic fibers, alumina fibers, silicon carbide fibers and the like can be used. Among these (D) inorganic fiber materials, those having a melting point of 1200 ° C. or less are preferable in terms of the strength of the ashed layer, and glass fibers are particularly preferable. (D)
The fiber length of the inorganic fiber material before compounding and kneading is not particularly limited, and commercially available fibers can be used. On the other hand, the fiber length of the inorganic fiber material (D) in the composition after compounding and kneading is not particularly limited, but is 0.05 to 2.0 mm.
Is preferable, and particularly preferably 0.1 to 1.5 mm. If the fiber length is less than 0.05 mm, the strength of the carbonized layer decreases at 600 ° C. or lower, and the strength of the ashed layer decreases at 600 ° C. or higher. If the fiber length exceeds 2.0 mm, the expansion ratio decreases. Is more likely to occur.

(E) The inorganic filler is not particularly limited, and any conventionally known non-fibrous filler can be used. Examples thereof include calcium carbonate, magnesium carbonate, fused silica,
At least one selected from the group consisting of crystalline silica, diatomaceous earth, clay, talc, mica, kaolin, titanium oxide, zinc oxide, aluminum oxide, carbon black, bentonite, aluminum hydroxide, and magnesium hydroxide
Preferably, a seed is used. When these inorganic fillers are used, when used together with the inorganic fiber material (D), the closed cell ratio of the expanded carbonized layer is improved, and a carbonized layer having excellent heat insulating properties is formed. Of these, non-sinterable inorganic fillers that do not harden at 1000 ° C. or lower are preferred. When such a non-sintering inorganic filler is used, shrinkage, cracking and cracking of the ashed layer are reduced when used together with the inorganic fiber material (D) having a melting point of 1200 ° C. or less, particularly Silica which has few cracks and cracks and has a high expansion ratio is preferred. Such silica is not particularly limited. For example, crystalline silica manufactured by Tatsumori Corporation (trade name “Crystalite A”)
A "), fused silica (trade name" Hugheslex E-2 "), amorphous silica (trade name" Imsil A-25 "), and the like.

The foam type fire-retardant composition of the present invention comprises (A) a thermoplastic resin, (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic fiber material, and (E) an inorganic filler. The composition further contains (F) a plasticizer. By containing (F) a plasticizer, a foaming type fire protection which is indispensable for foaming carbonization can contain (B) a phosphorus compound and (C) a polyfunctional alcohol in a larger amount, and is more excellent in fire resistance performance. Composition can be obtained. Further, the (F) plasticizer provides a high expansion ratio in order to appropriately lower the viscosity of the composition to prevent foam breakage and the like, and to prevent the shape retention (strength) of the carbonized layer from being reduced by moisture or water. He also has a role.

The plasticizer (F) is not particularly limited, and a general plasticizer can be used, but a plasticizer having good compatibility with the thermoplastic resin (A) is preferable. For example, at least one selected from the group consisting of polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, poly-α-olefins, paraffinic oil, naphthenic oil, α-methylstyrene oligomer, atactic polypropylene and the like is used. Is done. Among the above plasticizers, at least one selected from poly-α-olefins and polybutenes which do not inhibit foamed carbonization is preferred.

The amount of the plasticizer (F) is preferably 1 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin (A). (F) If the blending amount of the plasticizer exceeds 100 parts by weight, bleed-out is liable to occur, causing a problem in moldability, and the viscosity of the composition is too low. The problem that the foaming ratio of the layer decreases tends to occur.

Further, in addition to the above components, the foamable fire-retardant composition of the present invention may further comprise (G) an amino group-containing compound as an additional component. (G) 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 amino group-containing compound is not particularly limited, but (A) the thermoplastic resin 100
It is preferably 0.1 to 20 parts by weight based on parts by weight. If the compounding amount of the amino group-containing compound exceeds this range, the strength of the foamed carbonized film to be formed becomes insufficient, which is not preferable.

The foam type fire-retardant composition of the present invention comprises (A)
In addition to thermoplastic resin, (B) phosphorus compound, (C) polyfunctional alcohol, (D) inorganic fiber material, and (E) inorganic filler, (F) plasticizer, (G) amino group-containing compound, Furthermore, in addition to foaming aids, reinforcing agents, fillers, hindered phenol-based and hindered amine-based antioxidants, ultraviolet absorbers, light stabilizers, pigments, etc. Can be blended.

Examples of the foaming aid include chemical foaming agents such as expandable permiculite, azodicarbonamide and sodium bicarbonate-citric acid.

The most preferable composition of the foam type fire-retardant composition of the present invention is (A) 10 to 120 parts by weight of a phosphorus compound, (C) polyfunctional alcohol 5 based on 100 parts by weight of a thermoplastic resin. To 90 parts by weight, the total of (D) the inorganic fiber material and the (E) inorganic filler is 10 to 200 parts by weight, and the ratio of the (D) inorganic fiber material to the (E) inorganic filler (D / E) is 0.05 to 20. When (F) a plasticizer is further contained, it is preferable to add 1 to 100 parts by weight of the (F) plasticizer with respect to 100 parts by weight of the thermoplastic resin (A). F) The phosphorus compound (B) 10 to 120 based on 100 parts by weight of the total of the plasticizer
Parts by weight, (C) 5 to 90 parts by weight of a polyfunctional alcohol,
(D) Inorganic fiber material and (E) inorganic filler in total of 10
It is preferable that the ratio (D / E) of the inorganic fiber material to the inorganic filler (D) is 0.05 to 20 parts by weight.

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 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.

The use of the foam type fire-retardant composition of the present invention is not particularly limited. For example, the foam-type fire-retardant composition is adhered or laminated on a wall, a column, a beam, a door, a combustible material or the like, and has an insulating property when exposed to a flame. The foamed carbonized layer can be formed and used for the purpose of preventing and fireproofing the object.

[0039]

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 ratio) A sheet-like molded product of 20 × 20 × 2 mm was flamed on a bottom surface of the crucible by a gas burner from the lower portion of the crucible so that the temperature reached 3 minutes after the lower surface of the crucible was about 600 ° C. For 3 minutes, and the ratio was obtained as the ratio of the thickness of the carbonized sheet after the heating and foaming / the thickness before the heating and foaming.

(Water resistance) A sheet of 20 × 20 × 2 mm was immersed in warm water of 50 ° C. for 2 weeks, and the expanded state was heated in the same manner as in the above-mentioned expansion ratio test to measure the expansion ratio. Expansion ratio after immersion / Expansion ratio before immersion) × 1
00 was obtained, and 80% or more was evaluated as ○, and less than 80% as X.

(Ashing property) A 25 × 25 × 2 mm sheet was heated in an electric furnace at 800 ° C. for 1 hour, and the state of the ashed sheet was observed. There was no penetrating portion, and no cracks or cracks occurred. The sample was rated as 、, the penetration, cracks and cracks were observed, and the sample that did not maintain the shape was rated as ×. (Ashing layer strength) After heating a sheet of 25 × 25 × 2 mm in an electric furnace at 800 ° C. for 1 hour, the incinerated sheet is placed on a smooth horizontal surface, and the weight is placed on the ashing layer. 0.9g 2
A metal plate having a thickness of 5 mm × 25 mm × 0.8 mm was placed, and further 30 g and 50 g of weights were further placed on the metal plate to observe the state of the foamed carbon layer. When the weight was placed on the foamed carbonaceous layer for 30 seconds and 30 g and 50 g did not cause collapse (indentation, cracks, etc.) in 30 seconds, ○ indicates that the collapse occurred at 50 g but did not occur at 30 g.
A sample that collapsed at 30 g was judged as x. In the evaluation of the shape retention of the foamed carbonized layer, the foamed carbonized layer taken out of the furnace and used within 10 minutes was used.

(Production Example 1) [Styrene-isobutylene-
Production of Styrene Block Copolymer (SIBS)] After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, 456.1 mL of n-hexane (dried with molecular sieves) and 456.1 mL of butyl chloride (Molecular) 656.5m)
L, and the polymerization vessel was placed in a dry ice / methanol bath at −70 ° C. and cooled, and then Teflon (registered trademark) was placed in a pressure-resistant glass liquefaction sampling tube equipped with a three-way cock containing 232 mL (2871 mmol) of isobutylene monomer. The liquid sending tube was connected, and the isobutylene monomer was sent into the polymerization vessel under nitrogen pressure. 0.647 g (2.8 mmol) of p-dicumyl chloride and 1.22 g (14 mmol) of N, N-dimethylacetamide were added.
Next, 8.67 mL (79.1 mmol) of titanium tetrachloride was further added.
1) was added to initiate polymerization. After stirring at the same temperature for 1.5 hours from the start of the polymerization, about 1 mL of the polymerization solution was sampled from the polymerization solution for sampling. Subsequently, the styrene monomer 7 previously cooled to −70 ° C.
7.9 g (748 mmol), n-hexane 23.9 m
A mixed solution of L and 34.3 mL of butyl chloride was added into the polymerization vessel. 45 minutes after adding the mixed solution,
About 40 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 50,000 and Mw / Mn was 1.40, and the Mn of the block copolymer after styrene polymerization was 67,00.
0, and a block copolymer having Mw / Mn of 1.50 was obtained.

(Example 1) SIBS1 obtained in Production Example
00 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and melamine (manufactured by Nissan Chemical Company) 7 as an amino group-containing compound. 0.5 parts by weight, 35 parts of glass fiber (glass fiber) (manufactured by Nippon Electric Glass Co., Ltd .: chopped strand 03T-511) as an inorganic fiber material, 15 parts of silica (manufactured by Tatsumori Co., Ltd .: Crislatite AA) as an inorganic filler, 45 parts by weight of polybutene as a plasticizer (manufactured by Idemitsu Petrochemical Co., Ltd .: polybutene 300H) were melt-kneaded at 150 ° C by a lab plast mill and then press-molded at 150 ° C to a thickness of 2 mm. Foaming ratio, water resistance, ashing property of the obtained molded product,
And the ash layer strength was evaluated. Table 1 shows the results.

(Example 2) SIBS1 obtained in Production Example
00 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and melamine (manufactured by Nissan Chemical Company) 7 as an amino group-containing compound. 0.5 parts by weight, 50 parts of glass fiber (glass fiber) (manufactured by Nippon Electric Glass Co., Ltd .: chopped strand 03T-511) as an inorganic fiber material, 25 parts of silica (manufactured by Tatsumori Co., Ltd .: Crislatite AA) as an inorganic filler, Forty parts by weight of polybutene (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) as a plasticizer was melt-kneaded at 150 ° C. by a lab plast mill, and then press-molded at 150 ° C. to a thickness of 2 mm. Foaming ratio, water resistance, ashing property of the obtained molded product,
And the ash layer strength was evaluated. Table 1 shows the results.

(Example 3) SIBS1 obtained in Production Example
00 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and melamine (manufactured by Nissan Chemical Company) 7 as an amino group-containing compound. 0.5 parts by weight, 25 parts of glass fiber (glass fiber) (manufactured by Nippon Electric Glass Co., Ltd .: chopped strand 03T-511) as an inorganic fiber material, 50 parts of silica (manufactured by Tatsumori Co., Ltd .: Crislatite AA) as an inorganic filler, Forty parts by weight of polybutene (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) as a plasticizer was melt-kneaded at 150 ° C. by a lab plast mill, and then press-molded at 150 ° C. to a thickness of 2 mm. Foaming ratio, water resistance, ashing property of the obtained molded product,
And the ash layer strength was evaluated. Table 1 shows the results.

(Example 4) SIBS1 obtained in Production Example
00 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and melamine (manufactured by Nissan Chemical Company) 7 as an amino group-containing compound. 0.5 parts by weight, 10 parts of glass fiber (glass fiber) (manufactured by Nippon Electric Glass Co., Ltd .: Chopped Strand 03T-511) as an inorganic fiber material, and calcium carbonate (BF-300 manufactured by Shiraishi Industry Co., Ltd.) 35 as an inorganic filler
And 40 parts by weight of polybutene as a plasticizer (Polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) were melt-kneaded at 150 ° C. by a lab plast mill and then press-molded at 150 ° C. to a thickness of 2 mm. The foaming ratio, water resistance, ashing property, and ashing layer strength of the obtained molded article were evaluated. Table 1 shows the results.

(Example 5) SIBS1 obtained in Production Example
00 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as polyhydric alcohol, and glass fiber (glass fiber) (in Japan) as an inorganic fiber material Electric Glass Company: Chopped Strand 03
T-511) 50 parts, silica (Chrysatite AA, manufactured by Tatsumori) 25 parts as an inorganic filler, polybutene (polybutene 300H, manufactured by Idemitsu Petrochemical Co.) 40 as a plasticizer
The parts by weight were melt-kneaded at 150 ° C. with a Labo Plastomill and then press-molded at 150 ° C. to a thickness of 2 mm. The foaming ratio, water resistance, ashing property, and ashing layer strength of the obtained molded article were evaluated. Table 1 shows the results.

(Example 6) SIBS1 obtained in Production Example
00 parts by weight, 30 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 12 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, glass fiber (glass fiber) as an inorganic fiber material (Japan) Electric Glass Company: Chopped Strand 03
T-511) 20 parts, and 10 parts of silica (Cryslatite AA, manufactured by Tatsumori Co., Ltd.) as an inorganic filler were melt-kneaded at 150 ° C. in a Labo Plastomill, and then 2 mm at 150 ° C.
It was press-molded to a thickness. The foaming ratio, water resistance, ashing property, and ashing layer strength of the obtained molded article were evaluated. Table 1 shows the results.

(Example 7) 100 parts by weight of a styrene-ethylene-propylene-styrene block copolymer (SEPS: Septon 2007 manufactured by Kuraray Co., Ltd.), and Sumisafe PM (manufactured by Sumitomo Chemical) 50 as ammonium polyphosphate
Parts by weight, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a polyhydric alcohol, 7.5 parts by weight of melamine (manufactured by Nissan Chemical Industries, Ltd.) as an amino group-containing compound, and glass fiber (glass fiber) as an inorganic fiber material ( Nippon Electric Glass: Chopped strand 03T-511)
35 parts, 15 parts of silica (Cryslatite AA, manufactured by Tatsumori) as an inorganic filler, and 45 parts by weight of polybutene (Polybutene 300H, manufactured by Idemitsu Petrochemical Co.) as a plasticizer.
After melt-kneading at 0 ° C. with a Labo Plastomill, 15
It was press-molded at 0 ° C. to a thickness of 2 mm. The foaming ratio, water resistance, ashing property, and ashing layer strength of the obtained molded article were evaluated.
Table 1 shows the results.

(Example 8) 100 parts by weight of ethylene-vinyl acetate copolymer (EVA: Evaflex EV410 manufactured by DuPont-Mitsui Polychemicals), 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, 35 parts of glass fiber (glass fiber) (manufactured by Nippon Electric Glass Co., Ltd .: chopped strand 03T-511) as an inorganic fiber material, and silica (dragon) as an inorganic filler Morisha: Crislatite AA) 15
And 45 parts by weight of polybutene as a plasticizer (manufactured by Idemitsu Petrochemical Co., Ltd .: polybutene 300H) were melt-kneaded at 150 ° C by a lab plast mill, and then press-molded at 150 ° C to a thickness of 2 mm. The foaming ratio, water resistance, ashing property, and ashing layer strength of the obtained molded article were evaluated. Table 1 shows the results.

(Comparative Example 1) SIBS1 obtained in Production Example
00 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and melamine (manufactured by Nissan Chemical Company) 7 as an amino group-containing compound. 0.5 parts by weight, 40 parts by weight of polybutene as a plasticizer (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) at 150 ° C.
After melting and kneading with a Labo Plastomill at 150 ° C
Was press-formed to a thickness of 2 mm. The foaming ratio, water resistance, ashing property, and ashing layer strength of the obtained molded article were evaluated. Table 1 shows the results. After this sheet was heated in an electric furnace at 800 ° C. for 1 hour, no ash layer remained.

(Comparative Example 2) SIBS1 obtained in Production Example
00 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and melamine (manufactured by Nissan Chemical Company) 7 as an amino group-containing compound. 0.5 parts by weight, 50 parts of calcium carbonate (manufactured by Shiraishi Industry Co., Ltd .: BF-300) as an inorganic filler, and polybutene (manufactured by Idemitsu Petrochemical Co., Ltd .: polybutene 300) as a plasticizer
H) 40 parts by weight were melt-kneaded at 150 ° C. with a Labo Plastomill and then press-molded at 150 ° C. to a thickness of 2 mm. The foaming ratio, water resistance, ashing property, and ashing layer strength of the obtained molded article were evaluated. Table 1 shows the results. After the sheet was heated in an electric furnace at 800 ° C. for 1 hour, the incinerated component remained, but the shape was not maintained.

(Comparative Example 3) SIBS1 obtained in Production Example
00 parts by weight, 75 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 50 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and calcium carbonate (manufactured by Shiraishi Industry Co., Ltd .: BF) as an inorganic filler -300) 100 parts were melt-kneaded at 150 ° C. with a lab plast mill, and then press-molded at 150 ° C. to a thickness of 2 mm. Foaming ratio of the obtained molded product, water resistance,
The ashability and ash layer strength were evaluated. Table 1 shows the results.

[0056]

[Table 1] Comparative Example 1 containing no inorganic fiber material or inorganic filler
However, when the composition was exposed to a high temperature, no heat insulating layer remained as an ashing layer, and there was a problem in fire resistance in a high temperature range. In Comparative Example 3, in which no inorganic fiber material was used, the expansion ratio was low,
The ash layer did not retain its shape. Further, in Comparative Example 4 in which the contents of the phosphorus compound, the polyfunctional alcohol, and the inorganic filler were increased, it was found that the ashed layer maintained its shape but was inferior in strength.

On the other hand, in Examples 1 to 8 in which the inorganic fiber material and the inorganic filler were used in combination, the foaming ratio was slightly reduced as compared with Comparative Example 1 in which the inorganic fiber material and the inorganic filler were not blended. The ashed layer had high strength and no shrinkage or cracks were observed in the ashed layer, confirming that the ashed layer was excellent in fire resistance even in a high temperature range.

[0058]

The foamable fire-retardant composition of the present invention can be heated and / or heated by adding a phosphorus compound, a polyfunctional alcohol, an inorganic fiber material, and an inorganic filler to a thermoplastic resin.
Alternatively, it forms a carbonized (ashed) layer that is expanded and foamed by a flame and has high fire resistance and heat insulation properties, and has excellent fire resistance especially in high temperature range, and it is easy to form a large area sheet with high elasticity and strength. In addition, since it is excellent in moisture resistance and water resistance, it can be used for a long period of time, and it is not necessary to periodically replace the resin. Such a foam-type fire-resistant composition is an excellent material that 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 7/04 C08K 7/04 C08L 21/00 C08L 21/00 23/00 23/00 53/00 53 / 00 C09K 21/04 C09K 21/04 21/12 21/12 (72) Inventor Taizo Aoyama 4-13-10 Nishihata, Takasago-shi, Hyogo F-term (reference) 4H028 AA02 AA03 AA05 AA07 AA10 AA12 AA24 AA30 AA35 AA42 AB03 BA03 4J002 AA01W AB00Y AC00W AC03X AE05X BB00X BB06W BB13X BB17X BC09X BP00W CC164 CC184 CC194 DA016 DA037 DA058 DE107 DE137 DE146 DE147 DE237 DH048 DH058 DJ006 DJ007 DJ017 DJ037 DJ047 DJ057 DL09 EC019 EF009 ET009E009 EF009 EF009 EF009 FD0 0

Claims (14)

[Claims] (1) a thermoplastic resin, (B) a phosphorus compound,
A foamable fire-retardant composition comprising (C) a polyfunctional alcohol, (D) an inorganic fiber material, and (E) an inorganic filler. 2. The foam type fire-retardant composition according to claim 1, further comprising (F) a plasticizer. 3. The foam type fire-retardant composition according to claim 1, further comprising (G) an amino group-containing compound. 4. The total content (D + E) of (D) an inorganic fiber material and (E) an inorganic filler is (A) a thermoplastic resin (10).
0 to 100 parts by weight, and 10 to 200 parts by weight, and
The foam type fire retardant according to claim 1, 2 or 3, wherein the weight ratio (D / E) of (D) the inorganic fiber material and (E) the inorganic filler is 0.05 to 20. Composition. 5. The foam-type fire-retardant composition according to claim 1, wherein (A) the thermoplastic resin is a thermoplastic elastomer. 6. The foam-type fire-retardant composition according to claim 5, wherein the thermoplastic elastomer is a block copolymer. 7. The foam type fire-retardant composition according to claim 6, wherein the block copolymer comprises a block composed of an aromatic vinyl compound and a block composed of an olefin compound. 8. The foam type fire-retardant composition according to claim 7, wherein the block composed of an olefinic compound in the block copolymer is a block mainly composed of isobutylene. 9. The foam type fire-retardant composition according to claim 1, wherein (D) the inorganic fiber material is a material having a melting point of 1200 ° C. or less. 10. The foam type fire-retardant composition according to claim 9, wherein the inorganic fiber material (D) having a melting point of 1200 ° C. or less is glass fiber. (E) the inorganic filler is calcium carbonate,
Magnesium carbonate, fused silica, crystalline silica, diatomaceous earth,
Claim 1 or 2, which is at least one selected from the group consisting of clay, talc, mica, kaolin, titanium oxide, zinc oxide, aluminum oxide, carbon black, bentonite, aluminum hydroxide, and magnesium hydroxide.
The foam-type fire-retardant composition according to 3, 4, 9, or 10. 12. The foam type fire-retardant composition according to claim 1, wherein (E) the inorganic filler is non-sinterable. 13. The foam-type fire-retardant composition according to claim 12, wherein the non-sinterable inorganic filler is silica. 14. The method according to claim 1, wherein (F) the plasticizer is at least one selected from polyalphaolefins and polybutenes.
5. The foam-type fire-retardant composition according to any one of items 1 to 4.