JPH05171005A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which generates no halogen gas during burning and is excellent in abrasion resistance and flexibility by compounding a specific hydrogenated copolymer resin, a specific resin, a polyamide resin, and a hydrated metal compd. each in a specified amt. CONSTITUTION:The title compsn. comprises 1-pts.wt. resin compsn. comprising 97-50wt.% hydrogenated block copolymer resin of the formula: A- (B-A) n (wherein A is a polymer block consisting of monovinyl-substd. arom. hydrocarbon units; B is an elastomeric polymer block consisting of conjugated diene units; and n is 1-5) and 3-50wt.% polyamide resin, 0.1-30 pts.wt. at least one resin selected from the group consisting of an ethylene-glycidylmethyl acrylate copolymer resin, an ethylene-ethyl acrylate-maleic anhydride copolymer resin, a silane deriv. of an ethylene-acrylic ester copolymer resin, polymethyl methacrylate, and a carboxylic acid deriv. of an acrylic resin and 50-300 pts.wt. hydrated metal compd.

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 and cables, hoses, sheets and injection products, 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 requested not to generate such a halogen-based gas. 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, in order to impart flame retardancy,
Resin composites containing magnesium hydroxide, aluminum hydroxide, etc. have been put to practical use, but in reality, in order to obtain flame retardancy, it is necessary to fill a large amount of these hydrated metal compounds. However, there is a problem that the surface is easily scratched and the surface is easily worn by friction. In order to solve such a problem, in order to improve the compatibility between the resin and the inorganic substance so far, a method of adding an olefinic silane graftmer, a method of adding a dicarboxylic acid derivative or a dicarboxylic acid anhydride derivative, or A method of adding a silicone composition to impart surface activity to the composition, a wax,
A method of bleeding a surface-active agent on the surface has been proposed, but it has been insufficient in a field where surface scratch resistance and abrasion resistance are required.

[0003]

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.

[0004]

The flame-retardant resin of the present invention is a composition comprising the following components (a) to (d): (a) +
(b) 100 parts by weight (however, (a) :( b) = 97: 3 to 50:50)
To (c) 0.1 to 30 parts by weight and (d) 50.
To 300 parts by weight. (a) General formula A- (BA) n (where A is a monovinyl-substituted aromatic hydrocarbon polymer block, B is a conjugated diene elastomeric polymer block, and n is an integer of 1 to 5). ) Hydrogenated derivative of block copolymer resin represented by (b) Polyamide resin (c) Ethylene-glycidyl methyl acrylate copolymer resin, ethylene-ethyl acrylate-maleic anhydride copolymer resin, ethylene-acrylic ester copolymer resin 1 or 2 selected from silane derivatives, polymethylmethacrylate, and carboxylic acid derivatives of acrylic resins
One or more resins (d) Hydrated metal compound.

The component (a) of the present invention is added for the purpose of preventing the deterioration of the characteristics caused when the hydrated metal compound is filled in a large amount. The monomer of the polymer block A in the block copolymer of the general formula A- (BA) n used in the present invention is a monovinyl-substituted aromatic hydrocarbon, preferably styrene, such as α-methylstyrene. Is also used. The conjugated diene monomer in the polymer block B is preferably butadiene or isoprene, or may be a mixture of both.

The component (b) of the present invention is added for the purpose of improving the wear resistance of the composition. The polyamide resin used in the present invention includes nylon-4, nylon-6,
Nylon-11, Nylon-12, Nylon-6,6,
Nylon-6,10, Nylon-6,12, Nylon-
11,6 and copolymers of nylon-6 and nylon-6,6. If the amount of these components added is 3 parts by weight or less, 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, and the product becomes expensive, which is not practical.

The component (c) used in the present invention is added to improve the compatibility between the polyamide resin and the resin represented by the component (a) and the compatibility with the hydrated metal compound. Examples of the acrylic ester of the silane derivative of the ethylene-acrylic ester copolymer resin used in the present invention include ethyl acrylate, methyl acrylate, and methyl methacrylate. Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, allyltrimethoxysilane, and allyltriethoxysilane. Examples of the acrylic resin of the carboxylic acid derivative of the acrylic resin include polymethylmethacrylate, ethylene-methylmethacrylate copolymer, ethylene-methylacrylate copolymer, ethylene-ethylacrylate copolymer and the like. Examples of the carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid and the like. If the addition amount of these components is 0.1 parts by weight or less, the compatibility between the polyamide resin and other additives is poor and mechanical properties, particularly 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
_{O3 · 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. If the addition amount of these is 50 parts by weight or less, it is difficult to obtain a desired flame retardant effect, and if it is 300 parts by weight or more, mechanical properties such as tensile strength are deteriorated and extrusion processability is deteriorated.

As other additives, the flame-retardant composition of the present invention may optionally contain additives usually used, such as antioxidants, neutralizing agents, ultraviolet absorbers, antistatic agents, pigments, dispersants and lubricants. Materials, thickeners, foaming agents, metal deterioration inhibitors, 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.

[0010]

EXAMPLES Examples will be described below. The respective components were kneaded at an extrusion temperature of 200 to 240 ° C. using a different-direction twin-screw extruder in accordance with the compounding ratios shown in Table 1, and granulated. 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 and the inner diameter is
A tube having a diameter of 18 mm and a thickness of 1 mm was extruded to evaluate the extrudability.

[0011]

[Table 1]

Note 1: Asahi Kasei styrene-butadiene-block copolymer hydrogenated derivative 2: Shell Chemical Co. styrene-butadiene-block copolymer hydrogenated derivative 3: Sumitomo Chemical Industries ethylene-glycidyl methyl acrylate Copolymer 4: Ethylene-ethyl acrylate manufactured by Sumitomo Chemical Co., Ltd.
Maleic anhydride copolymer 5: ROHM & HAAS carboxylic acid derivative of acrylic resin 6: Kureha Chemical Industry polymethylmethacrylate 7: Mitsui DuPont Polychemical silane derivative of ethylene-ethyl acrylate copolymer resin 8: Showa Denko Hijilite H42M 9: Kyowa Chemical Kisuma 5B 10: Sanyo Chemical Co., Ltd. Sunwax 171P 1.0 parts by weight Ciba Geigy Irganox 1076 0.3 parts by weight Sumitomo Chemical Sumilizer WXR 0.3 parts by weight mixture 11: For pigment black: VALCAN 9A-32 3.0 parts by weight 12: According to JIS K6760 13: According to JIS K7201 14: Worn wheel CS-10, load 500g, 1000 rpm 15: 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.

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 polyamide resin, and have a phase of the polymer and the hydrated metal compound. It has very good solubility and shows very good workability and elongation at break. On the other hand, in Comparative Example 1, since no polyamide resin was added, wear resistance was poor, and in Comparative Example 2 in which the amount of polyamide resin added 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 is small, the flame retardancy is poor, and in Comparative Example 5 in which the addition amount of the hydrated metal compound exceeds 300 parts by weight, the workability is poor.

[0014]

As described above, according to the present invention,
It is possible to obtain a resin composition which does not generate a harmful halogen-based gas at the time of combustion, retains 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 77/00 LQS 9286-4J 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) General formula A- (BA) n (where A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5). ) Hydrogenated derivative of block copolymer resin represented by (b) Polyamide resin (c) Ethylene-glycidyl methyl acrylate copolymer resin, ethylene-ethyl acrylate-maleic anhydride copolymer resin, ethylene-acrylic ester copolymer resin 1 or 2 selected from silane derivatives, polymethylmethacrylate, and carboxylic acid derivatives of acrylic resins
One or more resins (d) hydrated metal compound.