JPH0593107A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which generates no halogen gas on burning, is flame-retardant and flexible, and has a remarkably improved abrasion resistance by compounding three specific resins and a hydrated metal compd. in a specified ratio. CONSTITUTION:The title compsn. is preped. by compounding 100 pts.wt. the sum of 97-50 pts.wt. at least one resin (A) selected from the group consisting of an ethylene-alpha-olefin copolymer and an ethylene-ethyl(or methyl) (meth)acrylate copolymer and 3-50 pts.wt. polyphenylene ether resin (B), 0.1-30 pts.wt. at least one resin (C) selected from the group consisting of a hydrogenated styrene- butadiene block copolymer, polymethyl methacrylate, a methyl acrylate- butadiene-styrene copolymer, an ethylene-ethyl acrylate-maleic anhydride copolymer, and a carboxylated acrylic resin, and 50-300 pts.wt. hydrated metal compd. (e.g. aluminum hydroxide) (D).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to be applied to coatings of electric wires and cables, hoses, sheets, injection products, etc., which do not generate harmful and corrosive halogen-based gas even when burned by a fire. And a flame-retardant resin composition.

[0002]

2. Description of the Related Art Conventionally, in order to impart flame retardancy to a polyolefin composition which has been widely used for coating electric wires, cables and the like, hoses, sheets, injection products, etc., a halogen compound and antimony trioxide are added to the polyolefin. It was achieved by adding. However, these compositions are halogen compositions, which are not preferable because they generate a halogen-based gas when burned, which is harmful to the human body and corrodes metals. Also, due to the large amount of smoke emitted and poor visibility, evacuation and extinguishing activities of people during a fire were significantly limited.

In particular, recently, from the viewpoint of safety, it has been strongly demanded that such a halogen-based gas should not be generated. In view of such circumstances, attention has been paid to inorganic flame retardants that use hydrated metal compounds that emit extremely little smoke and are less harmful. In recent years, resin composites containing magnesium hydroxide, aluminum hydroxide and the like have been put to practical use in order to impart flame retardancy, but actually, in order to obtain flame retardancy, these hydrated metal compounds are used. Since it is necessary to fill a large amount, there is a problem that the surface is easily scratched and the surface is easily worn by friction.

In order to solve the above problems and to improve the compatibility between the resin and the inorganic substance, a method of adding an olefinic silane graftmer, a method of adding a dicarboxylic acid derivative or a dicarboxylic acid anhydride derivative,
Alternatively, a method of adding a silicone composition for imparting surface activity to the composition, a method of bleeding a wax or a surfactant on the surface, and the like have been proposed. Particularly, scratch resistance of the surface and abrasion resistance are proposed. Was not enough in the required field.

[0005]

DISCLOSURE OF THE INVENTION The present invention does not generate harmful halogen-based gas upon combustion, does not lose the high flame retardancy obtained by adding a hydrated metal compound, and is flexible. The purpose of the present invention is to provide a flame-retardant resin composition that retains the above and has significantly improved abrasion resistance.

[0006]

The flame-retardant resin composition of the present invention is a composition comprising the following components (a) to (d), wherein (a) + (b) 100 parts by weight ( However, (a) :( b) = 97: 3
˜50: 50) and 0.1 to 30 parts by weight of (c) and
It is characterized by containing 50 to 300 parts by weight of (d). (a) one or more resins selected from a copolymer of ethylene and α-olefin, an ethylene-ethyl acrylate copolymer resin or an ethylene-methyl methacrylate copolymer resin, (b) a polyphenylene ether resin,
(c) Among hydrogenated derivatives of styrene-butadiene block copolymers, polymethyl methacrylate, methyl acrylate-butadiene-styrene copolymer resins, ethylene-ethyl acrylate-maleic anhydride copolymer resins, carboxylic acid derivatives of acrylic resins 1 or 2 or more types of resin selected from, and (d) hydrated metal compound.

The component (a) of the present invention is added for the purpose of preventing the deterioration of properties caused when a large amount of a hydrated metal compound is filled. Examples of the α-olefin of the copolymer of ethylene and α-olefin used in the present invention include C _{3 to} C ₁₂ such as propylene, butene-1,
Pentene-1, hexene-1, heptene-1, octene-1, 4-methylpentene-1, 4-methylhexene-
1,4,4-dimethylpentene-1, nonene-1, decene-1, undecene-1 and dodecene-1 and the like. Among these, ethylene-ethyl acrylate copolymer resin or ethylene-methyl methacrylate copolymer resin One or more resins selected from are used.

The component (b) of the present invention is added for the purpose of improving the wear resistance of the composition. Examples of the polyphenylene ether resin used in the present invention include poly (2,6-dimethylphenylene-1,4-ether) and poly (2,6-
Diethylphenylene-1,4-ether), poly (2-
Methyl-6-ethylphenylene-1,4-ether),
Poly (2-methyl-6-isopropylphenylene-1,
4-ether), poly (2,6-di-n-propylphenylene-1,4-ether), poly (2-methylphenylene-1,4-ether), poly (2-phenylphenylene-1,4-). Ether), poly (2-methyl-6-phenylphenylene-1,4-ether), poly (2-methyl-6-n-butylphenylene-1,4-ether) and the like. If the amount of these components added is 3 parts by weight or less in proportion to the component (a), it is difficult to obtain the desired effect of improving wear resistance, and if it is 50 parts by weight or more, flexibility and flame retardancy are deteriorated. Is not practical because it becomes expensive.

The component (c) used in the present invention is added to improve the compatibility between the polyphenylene ether resin and the resin represented by the component (a) and the compatibility with the hydrated metal compound. The acrylic resin of the carboxylic acid derivative of the acrylic resin used in the present invention includes polymethyl methacrylate, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer and the like. . The addition amount of these is (a) component + (b) component 1
When the amount is less than 0.1 parts by weight, the compatibility between the polyphenylene ether resin and other additives is poor, so that the mechanical properties, particularly the elongation, are poor. On the other hand, when the amount is 30 parts by weight or more, no remarkable effect exceeding the improving effect of the present invention is exhibited and the product becomes expensive, which is not practical.

The hydrated metal compound used in the present invention has a decomposition initiation temperature in the range of 150 to 450 ° C.,
A compound represented by the general formula M _m O _n · XH ₂ O (where M is a metal, m and n are integers of 1 or more determined by the valence of the metal, and X is a number of contained waters of crystallization), or a compound represented by the formula It is a double salt containing, specifically, aluminum hydroxide (Al ₂ O ₃ .3H ₂ O;
Or Al (OH) ₃ ), magnesium hydroxide (MgO · H ₂ O; or Mg (OH) ₂ ), calcium hydroxide (CaO · H ₂ O; or
Ca (OH) ₂ ), barium hydroxide (BaO ・ H ₂ O; or BaO ・ 9
H ₂ O), zirconium oxide hydrate (ZrO ・ nH ₂ 0), tin oxide hydrate (SnO ・ H ₂ 0), basic magnesium carbonate (3MgC
_{O 3 · Mg (OH) 2} · 3H 2 O), hydrotalcite (6MgO · Al ₂
O ₃ · H ₂ O), dawsonite (Na ₂ CO ₃ · Al ₂ O ₃ · nH ₂ O), borax (Na ₂ O · B ₂ O ₅ · 5H ₂ O), zinc borate (ZnB ₄ O ₇ · 2ZnO)
Etc. As for the amount of addition of these components, if the amount is 50 parts by weight or less relative to 100 parts by weight of the component (a) + the component (b), it is difficult to obtain the desired flame retardant effect. And the extrusion processability deteriorates.

As other additives, the flame-retardant composition of the present invention may optionally contain additives usually used, for example, antioxidants, neutralizing agents, ultraviolet absorbers, antistatic agents, pigments, dispersants, lubricants. Materials, thickeners, foaming agents, metal deterioration preventing agents, antifungal agents, flow regulators, etc., flame retardants of phosphorus and phosphine derivatives, other inorganic fillers, crosslinking agents, crosslinking aids, etc.,
Alternatively, other synthetic resin may be contained. It is also possible to carry out electron beam irradiation for crosslinking.

[0012]

EXAMPLES Examples will be described below. Among the compounding ingredients shown in Table 1, the components (a) (1 to 3), the polyphenylene ether resin and the component (c) (4 to 8) are kneaded at an extrusion temperature of 160 to 290 ° C. using a bidirectional extruder. And then granulated. A hydrated metal compound, a lubricant, a stabilizer and a pigment were added to the crude product thus obtained, and the mixture was kneaded at an extrusion temperature of 200 to 240 ° C. by using a bidirectional extruder of different directions to granulate. The obtained composition was roll-pressed to prepare various measurement test pieces. Using this test piece, tensile breaking elongation, oxygen index and wear test were carried out. Also, depending on the extruder, the outer diameter is 20 mmφ, the inner diameter is 18 mmφ,
A 1 mm-thick tube was extruded and the extrusion processability was evaluated.

[0013]

[Table 1]

(1) Nippon Petrochemical Softlex (ethylene-α-olefin copolymer) (2) Nippon Petrochemical Lexulon (ethylene-ethyl acrylate copolymer) (3) Sumitomo Chemical low density polyethylene ( 4) Asahi Kasei Co., Ltd. Maleic anhydride derivative of hydrogenated derivative of styrene-butadiene block copolymer (5) Sumitomo Chemical Co., Ltd. ethylene-ethyl acrylate-
Maleic anhydride copolymer (6) Carboxylic acid derivative of acrylic resin made by ROHM & HAAS (7) Polymethylmethacrylate made by Kureha Chemical Industry (8) Methyl acrylate-butadiene-styrene copolymer made by Kureha Chemical Industry (9) Showa Denko Heidilite H42M (10) Kyowa Chemical Kisuma 5B (11) Sanyo Chemical Co., Ltd.Sun Wax 171P 1.0 part by weight Ciba Geigy Irganox 1076 0.3 parts by weight
And Sumitomo Chemical's Sumilizer WXR 0.3 parts by weight (12) Pigment Black: VALCAN 9A-32 3.0 parts by weight (13) According to JIS K6760. (14) According to JIS K7201. (15) Worn wheel CS-10, load 500g, 1000 rotations. (16) 50mmφ single screw extruder 160-165-170-180 ℃ L / D: 25
Compression ratio 3.5 Tube extrusion Outer diameter 20 mmφ, Inner diameter 18 mmφ Evaluation Excellent>Good>Acceptable> Impossible, in order of acceptable level.

As is clear from Table 1, the materials shown in Examples 1 to 4 maintain flame retardancy, exhibit good abrasion resistance by the addition of the polyphenylene ether resin, and show the polymer and the hydrated metal compound. The compatibility is extremely good, and the workability and elongation at break values are very good. On the other hand, in Comparative Example 1, the abrasion resistance was poor because no polyphenylene ether resin was added, and in Comparative Example 2 in which the polyphenylene ether resin content was large, the flexibility was poor and the elongation at break value was also significantly reduced. . In Comparative Example 3 in which the component (c) as the compatibilizer was not added, the elongation at break value was significantly reduced. Further, in Comparative Example 4 in which the addition amount of the hydrated metal compound was small, the flame retardance was poor, and the addition amount of the hydrated metal compound was 300.
Comparative Example 5 in which the amount is more than parts by weight has poor workability.

[0016]

As described above, according to the present invention,
It is possible to obtain a resin composition that does not generate harmful halogen gas at the time of combustion, has a high degree of flame retardancy and flexibility, and has significantly improved abrasion resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 71/12 LQP 9167-4J H01B 3/30 P 9059-5G // H01B 7/34 B 7244- 5G

Claims (1)

[Claims] 1. A composition comprising the following components (a) to (d), wherein (a) + (b) 100 parts by weight (where (a) :( b) =
97: 3 to 50:50), 0.1 to 30 parts by weight of (c) and 50 to 300 parts by weight of (d) are contained in the flame-retardant resin composition. (a) one or more resins selected from a copolymer of ethylene and α-olefin, an ethylene-ethyl acrylate copolymer resin or an ethylene-methyl methacrylate copolymer resin, (b) a polyphenylene ether resin, (c) Among hydrogenated derivatives of styrene-butadiene block copolymers, polymethyl methacrylate, methyl acrylate-butadiene-styrene copolymer resins, ethylene-ethyl acrylate-maleic anhydride copolymer resins, carboxylic acid derivatives of acrylic resins 1 or 2 or more types of resin selected from, and (d) hydrated metal compound.