JP2002194225A - Foamable fireproof composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamable fireproof composition which expands and foams by heating and/or a fire to form a carbonized layer of high heat insulating properties to thereby exhibit an effect of fireproofing a combustible material or preventing a smoke, a flame, a gas generating by combustion, and the like from flowing out, with the effect free from a decrease due to water or moisture, i.e., exhibiting high water and moisture resistances, and which is excellent in formability into a sheet. SOLUTION: The composition contains (A) a thermoplastic resin, (B) a lubricant, (C) a phosphorus compound, and (D) a polyfunctional alcohol.

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 having excellent sheet formability and water resistance.

[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.

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 refractory rubber composition containing a rubber material, a phosphorus compound and a hydrocarbon compound having a hydroxyl group in the molecule. The fire resistance of such a fire-resistant composition is based on the fact that the phosphorus compound acts as a catalyst for dehydrating an organic substance, and in particular, dehydrates and carbonizes a hydrocarbon compound having a hydroxyl group, thereby forming a fire-resistant carbonized layer. However, phosphorus compounds and hydrocarbon compounds having a hydroxyl group in the molecule are:
When they are blended with rubber or thermoplastic resin, they tend to bleed out, so when forming this composition into a sheet, it becomes sticky to the surface of the calender roll, and it has poor moldability such as eyes and blemishes on the die part of the extruder. There was a problem.
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.

[0004]

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 a composition exhibiting fire resistance without bleeding out, having excellent sheet formability, and being heated by heating. An object of the present invention is to provide a fire-retardant composition having excellent water resistance and / or moisture resistance, in which a combustible is prevented by forming an expanded and foamed carbonized layer having a high shape retention (strength).

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, by adding a lubricant to a thermoplastic resin, the present invention has been found to be excellent in moldability into a sheet shape and to be heated. And / or expanded by a flame, to form a highly heat-insulating carbonized layer foamed, excellent in water resistance and / or moisture resistance,
A foamed fire-retardant composition having excellent elasticity and strength has been obtained. That is, the present invention relates to (A) a thermoplastic resin, (B)
A foam-type fire-retardant composition comprising a lubricant, (C) a phosphorus compound, and (D) a polyfunctional alcohol. The composition may further contain a plasticizer (E), and further comprise an amino group. The compound (F) may be contained.

[0006] The lubricant (B) is preferably at least one selected from ester type and fatty acid type.

[0007] The thermoplastic resin (A) is preferably a block copolymer, and the block copolymer is
A block composed of a block composed of an aromatic vinyl compound and a block composed of an olefin compound is more preferable. Further, the block composed of an olefin compound in the block copolymer is preferably a block mainly composed of isobutylene.

The (C) phosphorus compound is preferably at least one selected from the group consisting of phosphates, polyphosphates, phosphoric amides, and polyphosphoric amides.

(D) The polyfunctional alcohol is preferably at least one selected from monopentaerythritol, dipentaerythritol and tripentaerythritol.

(E) The plasticizer is preferably at least one selected from poly-α-olefins and polybutenes.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The foam type fire-retardant composition of the present invention comprises:
(A) a thermoplastic resin, (B) a lubricant, (C) a phosphorus compound,
And (D) a polyfunctional alcohol, and the mechanism of foaming and carbonization by heating and / or flame of the foaming type fire-retardant composition is chemically decomposed and reacted, although there is an unclear part. It is possible to form a stable, high-strength, heat-insulating carbonized layer.

(A) The thermoplastic resin is not particularly restricted but includes, for example, polyolefins such as polypropylene and polyethylene, polystyrene, ABS, MBS, acryl, polyurethane, polyvinyl chloride, polyester, polyamide, polyether, polybutadiene and styrene. −
At least one selected from the group consisting of block copolymers such as isoprene-styrene, natural rubber, butyl rubber, chloroprene rubber, and raw rubbers such as ethylene-propylene rubber can be used. Among the above thermoplastic resins, a block copolymer is preferable in terms of processability and sheet strength, and a resin composed of a block made of an aromatic vinyl compound and a block made of an olefin compound is particularly 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. Among the above compounds, styrene, α-methylstyrene, p-methylstyrene, and indene are preferable from the balance of cost, 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 these, a polyisobutylene block containing a large amount of tertiary carbon necessary for forming a stable and strong carbonized layer and having a high water vapor barrier property 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 a block composed of an aromatic vinyl-based compound and a block composed of an olefin-based compound is not particularly limited.
0 to 500,000 is preferred, and 40,000 to 4
00,000 is particularly preferred. Number average molecular weight of 30,00
When it is less than 0, mechanical properties and the like are not sufficiently exhibited, and when 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 10 to 40 parts by weight of the aromatic vinyl compound are more preferred.

The lubricant (B) improves the dispersibility of the phosphorus compound (C) and the polyfunctional alcohol (D) described later in the thermoplastic resin (A) serving as a binder, and acts as a compatibilizer. By doing so, the bleed-out of (C) and (D) is suppressed, and the formability into a sheet is improved. (B) The lubricant is not particularly restricted but includes, for example, hydrocarbons such as liquid paraffin, paraffin wax and low molecular weight polyethylene; fatty acids such as higher fatty acids and oxy fatty acids; amides such as fatty acid amides and alkylene bis fatty acid amides; Esters such as fatty acid butyl and fatty acid monoglyceride; alcohols such as polyethylene glycol, polyglycerol and stearyl alcohol; metal soaps such as fatty acid calcium, fatty acid magnesium and fatty acid zinc; montan wax, ivota wax,
At least one selected from the group consisting of natural waxes such as beeswax, modified waxes thereof, and silicones is used.

In order to efficiently disperse the non-polar (C) phosphorus compound and the (D) polyfunctional alcohol among the above lubricants, fatty acids, amides, esters,
Alcohols are preferred, and esters are particularly preferred.
Examples of the ester type include butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, hydrogenated castor oil, stearyl stearate, and phosphate esters, but are not particularly limited and at least one selected from the group consisting of these. Use
It is considered that the reason why the ester type is preferable is that the compatibility with the binder resin having low polarity is improved.

The blending amount of the lubricant (B) is not particularly limited, but is 0.1 to 60 parts by weight, preferably 0.5 to 40 parts by weight, per 100 parts by weight of the thermoplastic resin (A).
Parts by weight. (B) When the compounding amount of the lubricant is 60 parts by weight or more, the moldability is improved, but the sheet surface becomes sticky, and the foaming ratio of the carbonized layer is reduced, so that a carbonized layer having high heat insulating properties can be obtained. Problem.

(C) 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 (C) not only act as a catalyst for dehydrating and / or carbonizing organic substances in 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, thereby expanding the entire composition, and reducing 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 180 ° 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 (trade name “Sumisafe PM”) made of Sumitomo Chemical Co., Ltd. consisting of ammonium polyphosphate "), Coated ammonium polyphosphate (trade name" TERAGE C60 ") manufactured by Chisso Corporation.

The amount of the phosphorus compound (C) is not particularly limited, but is preferably 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 (D) is dehydrated by the phosphorus compound (C) 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.

(D) The blending amount of the polyfunctional alcohol 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 compounding amount of the polyfunctional alcohol component (D) falls below this range, the expansion will be insufficient, and conversely, (D)
If the compounding amount of the polyfunctional alcohol component exceeds this range, formation of the foamed carbon film becomes insufficient.

The foam type fire-retardant composition of the present invention comprises (A) a thermoplastic resin, (B) a lubricant, (C) a phosphorus compound, and (D) a polyfunctional alcohol. Compositions containing a plasticizer are preferred. (E) By containing a plasticizer, it is indispensable for foaming carbonization.
(C) The phosphorus compound and (D) the polyfunctional alcohol can be contained in a larger amount, and a foamed fire-resistant composition having more excellent fire resistance can be obtained. Furthermore, (E)
The plasticizer provides a high expansion ratio in order to appropriately lower the viscosity of the composition and prevent foam breakage, and also has a role of preventing the shape retention (strength) of the carbonized layer from being reduced by moisture or water. I have.

The plasticizer (E) is not particularly limited, and a general plasticizer can be used, but a plasticizer having good compatibility with the component (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, paraffin-based oil, naphthenic-based 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 (E) is preferably 1 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin (A). If the blending amount of the plasticizer (E) 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-mentioned components, the foamable fire-retardant composition of the present invention may further comprise (F) an amino group-containing compound as an additional component. (F) 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) lubricant, (C) phosphorus compound, and (D) polyfunctional alcohol, (E) plasticizer,
(F) an amino group-containing compound, and further, depending on the required characteristics according to each application, in addition to a foaming aid, a reinforcing agent, and a filler, a hindered phenol-based or hindered amine-based antioxidant or an ultraviolet absorber, A light stabilizer, a pigment and the like can be appropriately compounded.

Examples of the foaming auxiliary include chemical foaming agents such as expandable permiculite, azodicarbonamide and sodium hydrogen carbonate-citric acid.

The most preferable composition of the foam type fire-retardant composition of the present invention is thermoplastic resin (A) thermoplastic resin 1
With respect to 00 parts by weight, (B) 0.5 to 25 parts by weight of a lubricant, 10 to 100 parts by weight of a phosphorus compound (C), and (D) 5 to 70 parts by weight of a polyfunctional alcohol. Further, when the composition contains a plasticizer (E), it is preferable to add 1 to 100 parts by weight of the plasticizer (E) based on 100 parts by weight of the thermoplastic resin (A). E) Total of 10 plasticizers
(B) 0.5 to 25 parts by weight of a lubricant with respect to 0 parts by weight,
Most preferably, it is 10 to 120 parts by weight of (C) a phosphorus compound and 5 to 90 parts by weight of (D) a polyfunctional alcohol.

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 foamed fire-retardant composition of the present invention is not particularly limited. For example, the foamed fire-retardant composition is adhered or laminated on a wall, a column, a beam, a door, etc., and is insulated when exposed to a flame. And can be used for the purpose of preventing and fireproofing the object.

[0034]

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.

(Molding processability) The composition was kneaded and kneaded in advance with a Labo Plastomill and then cured at 100 ° C. for 2 hours. That is, those which could be taken out without any problem and could be made into sheets were evaluated as ○, and those which were adhered to the roll surface and had difficulty in workability such as taking up and turning back were evaluated as ×. The roll temperature was 100 ° C., the rotation speed was 14 rpm for the front, and 1 for the back.
The measurement was performed at 6 rpm and the clearance was 2 mm.

(Expansion Characteristics Test) A sheet-shaped molded product of 20 × 20 × 2 mm was heated on the bottom of the crucible by a gas burner from the bottom of the crucible to reach a temperature of about 600 minutes after the bottom of the crucible after 3 minutes.
It heated with the flame which becomes ° C, and observed the foaming state, and the foaming ratio was calculated | required as the ratio of the thickness of the carbonized sheet after heat foaming / thickness before heat foaming. The appearance of the formed carbonized foam layer was observed, and the shape retention was visually evaluated. That is, those in which the foamed carbonized layer maintained its shape without collapse were evaluated as ○, and those in which the foamed carbonized layer collapsed without maintaining its shape were evaluated as ×.

(Water Resistance Test) A 20 × 20 × 2 mm sheet was immersed in warm water at 50 ° C. for 2 weeks, and the foaming state was observed by heating in the same manner as in the foaming property test.

(Retention Ratio) The retention ratio was determined as (expansion ratio after immersion in warm water at 50 ° C. for 2 weeks / expansion ratio when not immersed in warm water at 50 ° C.) × 100.

(Production Example 1) [Styrene-isobutylene-
Production of Styrene Block Copolymer (SIBS)] After replacing the inside of the polymerization vessel of a 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. 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 of titanium tetrachloride (79.1 m
mol) was added to initiate polymerization. 1.5 from the start of polymerization
After stirring at the same temperature for a period of time, about 1 mL of the polymerization solution was withdrawn from the polymerization solution for sampling. continue,
77.9 g (748 mmol) of a styrene monomer previously cooled to -70 ° C, 23.9 n-hexane
A mixed solution of mL and 34.3 mL of butyl chloride was added to the polymerization vessel. Forty-five minutes after the addition of 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) SIBS obtained in Production Example 1
100 parts by weight, 10 parts by weight of wax OP (manufactured by Hoechst) as a lubricant, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical) as ammonium polyphosphate, and pentaerythritol (manufactured by Mitsubishi Gas Chemical) as a polyhydric alcohol 2
0 parts by weight, 7.5 parts by weight of melamine (manufactured by Nissan Chemical Industries, Ltd.) as an amino group-containing compound, and 15 parts by weight of 30 parts by weight of polybutene (polybutene 300H, manufactured by Idemitsu Petrochemical Company) 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 characteristics and the water resistance to the foaming characteristics of the obtained molded product were evaluated, and the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Example 2) SIBS obtained in Production Example 1
100 parts by weight, wax E as lubricant (made by Hoechst)
10 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, 7 melamine (manufactured by Nissan Chemical Company) as an amino group-containing compound 0.5 parts by weight and 30 parts by weight of polybutene (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) as a plasticizer 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 properties of the obtained molded articles and the water resistance against the foaming properties were evaluated, and the roll-formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Example 3) SIBS obtained in Production Example 1
100 parts by weight, 10 parts by weight of Farvac PL-1 (manufactured by NOF Corporation) as a lubricant, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, and pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol 20 parts by weight, 7.5 parts by weight of melamine as an amino group-containing compound (manufactured by Nissan Chemical Co., Ltd.), and 30 parts by weight of polybutene as a plasticizer (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) were melt-kneaded at 150 ° C. using a Labo Plastomill. Then, it was press-formed at 150 ° C. to a thickness of 2 mm. Evaluate the foaming properties of the obtained molded article and the water resistance against the foaming properties,
Further, the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Example 4) SIBS obtained in Production Example 1
100 parts by weight, wax E as lubricant (made by Hoechst)
20 parts by weight, 70 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, 30 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) as a polyhydric alcohol, and melamine (manufactured by Nissan Chemical Company) 12 as an amino group-containing compound 30 parts by weight of polybutene (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) as a plasticizer 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 properties of the obtained molded articles and the water resistance against the foaming properties were evaluated, and the roll-formability of the melt-blended composition was evaluated. Table 1 shows the results
Shown in

Example 5 SIBS obtained in Production Example 1
100 parts by weight, wax E as lubricant (made by Hoechst)
20 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 Co., Ltd.) as an amino group-containing compound 7 After melt-kneading 0.5 parts by weight at 150 ° C. with a lab plast mill, the mixture was press-formed at 150 ° C. to a thickness of 2 mm. The foaming characteristics and the water resistance to the foaming characteristics of the obtained molded product were evaluated, and the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Example 6) 100 parts by weight of styrene-ethylene propylene-styrene block copolymer (SEPS: Septon 2007 manufactured by Kuraray Co., Ltd.), 20 parts by weight of wax E (manufactured by Hoechst), and Sumisafe as ammonium polyphosphate PM (manufactured by Sumitomo Chemical) 50 parts by weight, pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) 20 parts by weight as a polyhydric alcohol, melamine (manufactured by Nissan Chemicals) 7.5 parts by weight as an amino group-containing compound, polybutene as a plasticizer (Idemitsu Petrochemical Co., Ltd .: Polybutene 300
H) 30 parts by weight were melt-kneaded at 170 ° C. with a lab plast mill and then press-molded at 170 ° C. to a thickness of 2 mm. The foaming characteristics and the water resistance to the foaming characteristics of the obtained molded product were evaluated, and the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Example 7) SIBS obtained in Production Example 1
100 parts by weight, wax E as lubricant (made by Hoechst)
10 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 polybutene as a plasticizer (polybutene 300H by Idemitsu Petrochemical Co., Ltd.) ) 30 parts by weight 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 characteristics and the water resistance to the foaming characteristics of the obtained molded product were evaluated, and the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Example 8) SIBS1 obtained in Production Example
00 parts by weight, wax E (made by Hoechst) 2 as a lubricant
0 parts by weight, Sumisafe P as ammonium polyphosphate
After melt-kneading 50 parts by weight of M (manufactured by Sumitomo Chemical Co., Ltd.) and 20 parts by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a polyhydric alcohol at 150 ° C. using a lab plast mill, the mixture was press-formed at 150 ° C. to a thickness of 2 mm. Evaluate the foaming properties of the obtained molded article and the water resistance against the foaming properties,
Further, the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Comparative Example 1) SIBS obtained in Production Example 1
100 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, and pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) 20 as polyhydric alcohol
Weight part, 7.5 parts by weight of melamine (manufactured by Nissan Chemical Industries, Ltd.) as an amino group-containing compound, and 30 parts by weight of polybutene (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.) as a plasticizer are 150 parts by weight.
After melting and kneading in a lab plast mill at 150 ° C.,
It was press-formed at 2 ° C. to a thickness of 2 mm. The foaming characteristics and the water resistance to the foaming characteristics of the obtained molded product were evaluated, and the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

(Comparative Example 2) SIBS obtained in Production Example 1
100 parts by weight, 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, and pentaerythritol (manufactured by Mitsubishi Gas Chemical Company) 20 as polyhydric alcohol
After melt-kneading 7.5 parts by weight of melamine (manufactured by Nissan Chemical Industries, Ltd.) as an amino group-containing compound at 150 ° C. with a lab plast mill, the mixture was press-formed at 150 ° C. to a thickness of 2 mm. The foaming characteristics and the water resistance to the foaming characteristics of the obtained molded product were evaluated, and the roll formability of the melt-blended composition was evaluated. Table 1 shows the results.

Comparative Example 3 100 parts by weight of SEPS (Septon 2007 manufactured by Kuraray Co., Ltd.), 50 parts by weight of Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) as ammonium polyphosphate, and pentaerythritol (Mitsubishi Gas Chemical Company) as a polyhydric alcohol 20 parts by weight, melamine as an amino group-containing compound (7.5 parts by weight, manufactured by Nissan Chemical Co., Ltd.), and polybutene as a plasticizer (polybutene 300H, manufactured by Idemitsu Petrochemical Co., Ltd.)
After melt-kneading 30 parts by weight at 170 ° C.,
It was press-formed at 2 ° C. to a thickness of 2 mm. The foaming characteristics and water resistance to the foaming characteristics of the obtained molded product were evaluated. Table 1 shows the results.

[0052]

[Table 1]

[0053]

[Table 2] As shown in Tables 1 and 2, Examples 1 to 8 in which a lubricant was added to Comparative Examples 1 to 3, which had high foaming and high water resistance but had poor roll processability, respectively, exhibited a slight decrease in the expansion ratio. Despite that, the workability is improved and the magnification ratio is 9
It was confirmed that the water resistance was not reduced to 0% or more, and that the foamed carbonized layer maintained a strong and stable shape. Thus, it was confirmed that the processability of the resin composition containing a large amount of the phosphorus compound or the polyfunctional alcohol was greatly improved by adding the lubricant.

[0054]

The foamable fire-retardant composition of the present invention has excellent moldability and facilitates the formation of a large-area sheet despite the large amount of the phosphorus compound or polyfunctional alcohol added. It is excellent in moisture resistance and water resistance, so that 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,
It is an excellent thing 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) C08L 23/02 C08L 23/02 F-term (Reference) 4J002 AE03Y BB01X BB17X BP01W BP02W DH047 EG036 EH026 EH046 EH056 ER028 ET188 EU EW046 EW047 FD02X FD137 FD17Y FD176 FD208

Claims (10)

[Claims] (A) a thermoplastic resin, (B) a lubricant, and (C)
A foam-type fire-retardant composition comprising a phosphorus compound and (D) a polyfunctional alcohol. 2. The foam-type fire-retardant composition according to claim 1, further comprising (E) a plasticizer. 3. The foam type fire-retardant composition according to claim 1, further comprising (F) an amino group-containing compound. 4. The foam-type fire-retardant composition according to claim 1, wherein (B) the lubricant is at least one lubricant selected from an ester type and a fatty acid type. 5. The foam-type fire-retardant composition according to claim 1, wherein (A) the thermoplastic resin is a block copolymer. 6. The foam-type fire-retardant composition according to claim 5, wherein the block copolymer comprises a block composed of an aromatic vinyl compound and a block composed of an olefin compound. 7. The foam type fire-retardant composition according to claim 6, wherein the block composed of an olefinic compound in the block copolymer is a block mainly composed of isobutylene. 8. The foam-type fire-retardant composition according to claim 1, wherein the phosphorus compound (C) is at least one selected from the group consisting of phosphates, polyphosphates, phosphoric amides, and polyphosphoric amides. 9. The foam type fire-retardant composition according to claim 1, wherein (D) the polyfunctional alcohol is at least one selected from monopentaerythritol, dipentaerythritol, and tripentaerythritol. 10. The method according to claim 2, wherein (E) the plasticizer is at least one selected from polyalphaolefins and polybutenes.
3. The foam type fire-retardant composition according to item 1.