JPH09227716A - Fire-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fire-resistant resin composition exhibiting remarkable fire-resisting performance owing to its flame-retardancy and the formation of a combustion residue having sufficient shape-retainability. SOLUTION: This resin composition is composed of a thermoplastic resin containing a phosphorus compound, a neutralized heat-expandable graphite and an inorganic filler. The amount of the sum of the phosphorus compound and the neutralized heat-expandable graphite is 20-200 pts.wt. and that of the inorganic filler is 50-500 pts.wt. based on 100 pts.wt. of the thermoplastic resin and the weight ratio of the neutralized heat-expandable graphite to phosphorus compound is 9:1 to 1:100.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fire resistant resin composition.

[0002]

2. Description of the Related Art In the field of building materials, conventionally,
Fire resistance is important. In recent years, resin materials have been widely used as building materials with the expansion of applications of the resin materials, and resin materials having fire resistance have been demanded.

For such fire resistance, not only the material itself is not easily burned, but also a property that the flame is not turned to the back side is required. Since the resin component and the organic component essentially have the property of burning or melting, there are problems such as how long such a state does not occur, and how long the contained inorganic component does not fall off.

Japanese Patent Application Laid-Open No. 6-25476 discloses a technique using red phosphorus or a phosphorus compound and thermally expandable graphite as a polyolefin resin. Although this product has sufficient flame retardancy, for example, when it is used in the form of a sheet as a wall lining material, only fragile ash remains in the fireproof and fireproof tests, and the residue may fall off or The temperature is 2
There was a problem that the temperature rose to 60 ° C. or more.

[0005]

SUMMARY OF THE INVENTION In view of the above, the present invention is a fire-resistant resin that exhibits flame-retardant properties, and that the residue after burning has a sufficient shape-retaining ability, thereby exhibiting remarkable fire-resistant performance. It is intended to provide a composition.

[0006]

Means for Solving the Problems The gist of the present invention is that a thermoplastic resin contains a phosphorus compound, a neutralized thermally expandable graphite, and an inorganic filler in constituting a refractory resin composition. The total content of the phosphorus compound and the neutralized thermally expandable graphite is 20 to 200 parts by weight, and the content of the inorganic filler is 50 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. It is assumed that 500 parts by weight, and the weight ratio of the neutralized heat-expandable graphite: phosphorus compound is 9: 1 to 1: 100. Hereinafter, the present invention will be described in detail.

The refractory resin composition of the present invention comprises a thermoplastic resin containing a phosphorus compound, neutralized thermally expansive graphite, and an inorganic filler. The thermoplastic resin is not particularly limited, for example, polypropylene resin,
Polyolefin resin such as polyethylene resin, poly (1-) butene resin, polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin , Polyvinyl chloride resins and the like. Among them, polyolefin resin is preferable, and polyethylene resin is more preferable.

Examples of the polyethylene resin include ethylene homopolymers, copolymers containing ethylene as a main component, mixtures thereof, ethylene-vinyl acetate copolymers, ethylene-ethylene acrylate copolymers and the like. . Examples of the copolymer containing ethylene as a main component include ethylene-α-olefin copolymers containing an ethylene portion as a main component, and examples of the α-olefin include 1-hexene and 4-methyl- 1-Pentene, 1-octene, 1-butene, 1-pentene and the like can be mentioned.

These ethylene and ethylene and α-olefins other than ethylene are polymerized using a Ziegler-Natta catalyst, a vanadium catalyst and a metallocene compound containing a tetravalent transition metal as a polymerization catalyst. In particular, a polyethylene resin obtained by polymerization using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst is preferable.

Using the metallocene compound containing a tetravalent transition metal as a polymerization catalyst, ethylene and α other than ethylene are used.
In the polymerization reaction for obtaining an olefin copolymer, the tetravalent transition metal is not particularly limited, and examples thereof include titanium and
Examples include zirconium, hafnium, nickel, palladium, platinum and the like.

The above-mentioned metallocene compound means a compound in which one or more cyclopentadienyl rings and their analogs are present as one or more ligands in the above tetravalent transition metal. The polyethylene resin obtained by the polymerization reaction using the metallocene compound as a polymerization catalyst is, for example, manufactured by Dow Chemical Co., Ltd., trade name “CGCT”, “Affinity”, “Engage”, Exxon Chemical Co., trade name “EXACT”. Commercially available products such as The above thermoplastic resins may be used alone or in combination of two or more.

Further, any of the above-mentioned thermoplastic resins may be used after being crosslinked or modified so long as the fire resistance of the resin composition is not impaired. In this case, pre-crosslinked, modified resin may be used, the phosphorus compound of the present invention, an inorganic filler,
It may be cross-linked or modified at the same time when other additives are added, or cross-linked after adding the above components to the resin,
It may be modified. The method for crosslinking the resin is also not particularly limited, and a general method for crosslinking a thermoplastic resin, for example,
Examples include various crosslinking agents, crosslinking using a peroxide, and crosslinking by electron beam irradiation.

The thermoplastic resin used in the present invention contains a phosphorus compound, neutralized thermally expansive graphite, and an inorganic filler. The fire resistance performance of the fire resistant resin composition of the present invention is expressed by these three components exhibiting their respective properties. Specifically, at the time of heating, the heat-expandable graphite forms an expanded heat-insulating layer to prevent the transfer of heat. Inorganic fillers then increase the heat capacity. The phosphorus compound has an ability to retain the shape of the expanded heat insulating layer and the filler.

The phosphorus compound is not particularly limited,
For example, red phosphorus; various phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylendiphenyl phosphate; phosphorus such as sodium phosphate, potassium phosphate, and magnesium phosphate Acid metal salts; ammonium polyphosphates; and compounds represented by the following general formula (1). Among them, ammonium polyphosphates; compounds represented by the following general formula (1) are preferable.

[0015]

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In the formula, R ¹ and R ³ are hydrogen, C ¹ -C 1
It represents a linear or branched alkyl group having 6 or an aryl group having 6 to 16 carbon atoms. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, Represents an aryloxy group represented by Formulas 6 to 16.

As the above-mentioned red phosphorus, commercially available red phosphorus can be used, but from the viewpoints of moisture resistance and safety such as not spontaneously igniting during kneading, those obtained by coating the surface of red phosphorus particles with a resin are preferable. .

As the above-mentioned ammonium polyphosphates,
Examples thereof include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and the like, and ammonium polyphosphate is preferable from the viewpoint of handleability and the like. Examples of commercially available products include “AP422” and “AP462” manufactured by Hoechst, “Sumisafe P” manufactured by Sumitomo Chemical Co., Ltd., and “Terrage C60” manufactured by Chisso.

Examples of the compound represented by the above general formula (1) include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid,
Propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphine Examples include acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis (4-methoxyphenyl) phosphinic acid. The above phosphorus compounds may be used alone or in combination of two or more.

The heat-expandable graphite used in the present invention is a conventionally known substance, and powders of natural scaly graphite, pyrolytic graphite, Kish graphite, etc. are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, selenic acid and concentrated nitric acid, A graphite intercalation compound is produced by treatment with a strong oxidizer such as perchloric acid, perchlorate, permanganate, dichromate, hydrogen peroxide, etc., while maintaining the carbon layer structure. Is a crystalline compound of.

In the present invention, the heat-expandable graphite obtained by the acid treatment as described above is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like. As the aliphatic lower amine, for example, monomethylamine, dimethylamine, trimethylamine,
Examples thereof include ethylamine, propylamine and butylamine. Examples of the alkali metal compound and alkaline earth metal compound include hydroxides, oxides, carbonates, sulfates, and organic acid salts of potassium, sodium, calcium, barium, magnesium and the like. Specific examples of the heat-expandable graphite thus neutralized include, for example, “CA-60S” manufactured by Nippon Kasei Co., Ltd., and “GR” manufactured by Tosoh Corporation.
EP-EG "and the like.

The particle size of the neutralized thermally expandable graphite used in the present invention is preferably 20 to 200 mesh. If the particle size is smaller than 200 mesh, the degree of expansion of graphite is small, the desired refractory insulation layer cannot be obtained, and if the particle size is larger than 20 mesh, there is an effect in that the degree of swelling is large, but when kneading with the resin, Poor dispersibility and inevitable deterioration of physical properties.

The inorganic filler used in the present invention is not particularly limited, and examples thereof include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites.
Calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, donnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc , Clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber,
Glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate "MOS", lead zirconate titanate, Examples include aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydrated sludge, and the like. These may be used alone or as a mixture of two or more.

Among the above-mentioned inorganic fillers, the hydrous inorganic substance has the property of dehydrating and absorbing heat when heated, which is advantageous in enhancing heat resistance. Specific examples include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. In addition, a metal salt or oxide of a metal belonging to Group II or Group III of the periodic table has a property of foaming to form a foamed fired product at the time of combustion, and thus is preferable for improving shape retention. Specific examples include calcium carbonate and magnesium carbonate.

In the present invention, the thermoplastic resin 10
The total amount of the phosphorus compound and the neutralized thermally expandable graphite is 20 to 200 parts by weight, and the inorganic filler is contained in an amount of 50 to 500 parts by weight based on 0 parts by weight. When the total amount of the phosphorus compound and the neutralized thermally expandable graphite is less than 20 parts by weight, sufficient fire resistance cannot be obtained,
When it exceeds 200 parts by weight, the mechanical properties are largely deteriorated,
Since it cannot be used, it is limited to the above range. Also,
If the amount of the inorganic filler is less than 50 parts by weight, sufficient fire resistance cannot be obtained, and if it exceeds 500 parts by weight, the mechanical properties are largely deteriorated and it cannot withstand use.

In the present invention, by combining neutralized heat-expandable graphite and a phosphorus compound, scattering of the heat-expandable graphite at the time of combustion is suppressed and shape retention is achieved.
If the amount of thermally expandable graphite is too large, the expanded graphite will scatter during combustion, and a sufficient expanded heat insulating layer will not be obtained at the time of heating. Conversely, if there is too much phosphorus compound, the heat insulating layer will not be sufficient and the desired effect will be obtained. Since it cannot be obtained, the weight ratio of the neutralized thermal expansion graphite and the phosphorus compound is 9: 1 to 1: 100 of the neutralized thermal expansion graphite: phosphorus compound.

From the viewpoint of shape retention during combustion, neutralized thermal expansion graphite: phosphorus compound = 1: 3.
The range of １ ： 1: 100 is excellent. Even if the composition itself is flame-retardant, if the shape-retaining property is insufficient, the residue that becomes brittle collapses and penetrates the flame. Therefore, depending on whether the shape-retaining property is sufficient, the refractory composition The usage forms of are very different. More preferably, the neutralized thermal expansion graphite: phosphorus compound = 1: 5 to 1:60, and particularly preferably 1:10 to 1:40.

The fire-resistant resin composition of the present invention further comprises a phenol-based, amine-based, and
Sulfur-based antioxidants, metal damage inhibitors, antistatic agents,
Stabilizers, crosslinking agents, lubricants, softeners, pigments and the like may be added.

The refractory resin composition of the present invention can be obtained by kneading the above components using a kneading device such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, or a roll.

[0030]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Ultra-low density polyethylene (denoted as VLDPE1 in Table 1) (density = 0.920, MI = 3.0) was neutralized with thermally expandable graphite (GREP-EG, Tosoh Corporation). Made),
Ammonium polyphosphate (Sumisafe P, Sumitomo Chemical Co., Ltd.), t-butylphosphonic acid (Wako Pure Chemical Industries, Ltd.), aluminum hydroxide (B703S, Nippon Light Metal Co., Ltd.), magnesium hydroxide (Kisuma 5B, Kyowa Chemical Co., Ltd.) In the blending ratio shown in Table 1, each component was melt-kneaded using a roll to obtain a resin composition. The resin composition obtained is heated to 140 ° C.
Then, a test piece used for fire resistance evaluation and shape retention evaluation was prepared.

<Evaluation of fire resistance> Length 100 mm, width 100
35 kW using a cone calorimeter (CONE2A, manufactured by Atlas) on a test piece having a thickness of 3.0 mm and a thickness of 3.0 mm.
/ M ² (horizontal direction) for 30 minutes, and the sample having a temperature of 260 ° C. or less on the rear surface (heating surface) of the test piece was evaluated as ○, and the sample over 260 ° C. was evaluated as x. The results are shown in Table 1.

<Evaluation of Shape Retention> A test piece (residue) after the above fire resistance evaluation has a length of 50 mm, a width of 50 mm and a thickness of 1 m.
m and a weight of 10 g and 50 g were placed on the metal plate, and the state of the residue was observed. In both 10 g and 50 g, ◎ indicates that the residue did not collapse (indentation, cracking, etc.), and ○ indicates that 50 g of the residue collapsed but did not collapse at 10 g. The results are shown in Table 1.

A shape-retaining evaluation of x is extremely brittle, and it collapses when the test piece is laid in the longitudinal direction. When actually used as a refractory material, it falls off during combustion. It is expected that the fire resistance will be developed in a short time.

Examples 2 to 6 and Comparative Examples 1 to 3 Melt kneading was carried out by using the rolls with the blending components and blending ratios shown in Table 1 to obtain resin compositions. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1, and fire resistance and shape retention were evaluated. The results are shown in Table 1. However, since the composition of Comparative Example 3 could not be molded into a putty, it was applied to the size of the test piece and evaluated.

In Table 1, VLDPE2 has a density of 0.90.
7, VL represents ultra low density polyethylene with MI = 3.0, VL
DPE3 represents ultra low density polyethylene with a density of 0.910 and MI = 2.0, and LDPE has a density of 0.92.
Low density polyethylene of 0, MI = 7.0, liquid chloroprene represents HO50 manufactured by Denki Kagaku.

[0037]

[Table 1]

[0038]

EFFECTS OF THE INVENTION The fire-resistant resin composition obtained by the present invention has a remarkable heat resistance by forming an expansion heat insulating layer upon heating and maintaining its shape, and can be provided for a wide range of applications. Is. Further, since the refractory resin composition itself can be molded, the fire resistance can be easily imparted by, for example, forming it into a sheet shape and coating it on a building or the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical display location C08L 101/00 C08L 101/00 (72) Inventor Kenji Inai 2 Hyakusan, Shimamoto-cho, Mishima-gun, Osaka Prefecture -1 Sekisui Chemical Co., Ltd.

Claims (5)

[Claims] 1. A thermoplastic resin containing a phosphorus compound, neutralized heat-expandable graphite, and an inorganic filler, the content of each of which is 100 parts by weight of the thermoplastic resin. , The total amount of the phosphorus compound and the neutralized thermally expandable graphite is 20 to 200 parts by weight, and the inorganic filler is 50 to 50 parts by weight.
500 parts by weight, the weight ratio of the neutralized heat-expandable graphite: phosphorus compound is 9: 1 to 1: 100, a refractory resin composition. 2. The refractory resin composition according to claim 1, wherein the weight ratio of the neutralized thermal expansion graphite: phosphorus compound is 1: 3 to 1: 100. 3. The fire resistant resin composition according to claim 1, wherein the phosphorus compound is ammonium polyphosphate. 4. The refractory resin composition according to claim 1, wherein the inorganic filler is a water-containing inorganic substance. 5. The inorganic filler is a group II or III of the periodic table.
The refractory resin composition according to any one of claims 1 to 4, which is a metal salt or oxide of a metal belonging to the family.