JPH06102743B2 - Flame-retardant olefin resin composition - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a flame-retardant olefin resin composition that does not generate any halogen-based harmful and corrosive gas even when burned due to a fire, and is particularly applied to electric wires and cables.

[Prior art]

Conventionally, in order to impart flame retardancy to a polyolefin composition that has been widely used as an insulating material for electric products such as electric wires and cables, it has been achieved by adding a halogen compound and antimony trioxide to the polyolefin. However, these compositions are halogen-based compositions and are harmful to the human body because halogenated gas is generated during combustion.
Moreover, the metal is corroded, which is not preferable. In addition, due to the large amount of smoke 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 desired not to generate such a halogen-based gas. In view of such circumstances, attention has been paid to inorganic flame retardants, which are hydrated metal compounds with extremely low smoke emission and toxicity. In recent years, in order to impart flame retardancy, resin composites have been filled with a large amount of magnesium hydroxide, aluminum hydroxide, etc., but magnesium hydroxide reacts with moisture and carbon dioxide in the air to give magnesium carbonate. And the crystalline white matter of magnesium carbonate is formed on the surface of the resin composition. Magnesium hydroxide and aluminum hydroxide are acid,
The chemical resistance of alkali is extremely poor, and it easily dissolves and elutes from the surface of the resin composition. In particular, it is remarkably eluted even with a weak acid such as PH2, which easily causes surface alteration. The surface is easily scratched due to the large amount of inorganic filler. When bent, the surface becomes white and buckles. However, there have been problems such as the above, which has been a cause of delaying the practical use of electric cables. However, as already mentioned in Japanese Patent Application No. 61-129064 and Japanese Patent Application No. 61-138316 in connection with the present invention, the silane grafter does not require any catalyst for accelerating the cross-linking and does not require hydration. Hydroxyl group (OH group) on the surface of metal compound and silanol group of silane grafter Is due to the influence of a slight amount of water on the surface of the hydrated metal compound and the hydrated metal compound similar to the catalyst of the organometallic compound, a condensation reaction due to hydrolysis occurs in the environment of frictional heat generated during kneading,
It forms a strong siloxane bond (-Si-O-MmOn; M is a metal). At this time, no catalyst or the like is needed. Due to this strong bond, the above-mentioned Japanese Patent Application Nos. 61-129064 and 61-138316 have excellent shape retention at high temperatures, prevent drip during combustion, and have mechanical whitening properties such as bending whitening and friction. It is clearly stated that it is effective in improving sex. Further, the examples also describe the improvement of mechanical characteristics, surface characteristics, thermal characteristics including heat deformation, and combustion characteristics such as oxygen index. Conventionally, liquid hydrocarbons such as polyethylene, polypropylene, ethylene vinyl acetate copolymers, copolymers of ethyl and α-olefins such as ethylene ethyl acrylate and liquid polybutadiene are used as skeletons, and maleic anhydride is used as peroxides. There are unsaturated dicarboxylic acid modified products obtained by reacting with a radical generator, and many are sold in Japan. In addition, many findings have been announced regarding the use of these to provide adhesiveness with other resins and adhesiveness with metallic inorganic powders, and there are numerous patent applications related to this. For example, Japanese Examined Japanese Patent Publication No.
88 and Japanese Patent Publication No. 62-9135. Further, as seen in JP-A-62-10151 and JP-A-62-11745, maleic anhydride is added to a copolymer of ethylene and α-olefin with peroxide or the like to prepare a composition. There are also examples of improved heat resistance and mechanical strength. These simply add a polar group of maleic anhydride to a non-polar resin, increase the affinity with the filler, and ultimately result in improving the mechanical strength and heat resistance, It is not intended to focus on the hydrated metal compound and to bond by moisture, that is, bond by forming a siloxane bond of a silane graftmer and forming a complex salt based on a reaction of a dicarboxylic acid anhydride derivative.

[Problems to be Solved by the Invention]

In order to solve the above problems, the inventors of the present invention have made a flame-retardant flame-retardant comprising an olefin resin, a silane graftmer of an olefin resin preliminarily silane-grafted, a hydrated metal compound and a dicarboxylic acid derivative or a dicarboxylic acid anhydride derivative. Although an olefin-based resin composition has been proposed (Japanese Patent Application No. 62-45200), the present invention occurs during various environmental tests by including a hydrated metal compound useful as a flame retardant, or in actual use. Provided is a flame-retardant resin composition which prevents the deterioration of the surface of these resin compositions and the significant decrease in chemical resistance, and further improves the scratches on the surface, the surface whitening and the buckling during bending by one layer. is there.

[Means for Solving the Problems]

The present invention is a composition comprising the following components (a) to (e), wherein (c) is added to 100 parts by weight of (a) + (b):
0.1 to 30 parts by weight, (d) 0.1 to 30 parts by weight and (e)
The flame-retardant olefin resin composition is characterized by containing 50 to 300 parts by weight. (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) Silane grafted in advance Silane grafter of olefin resin (c) Maleic anhydride grafted product of polyethylene, maleic anhydride grafted product of ethylene-vinyl acetate copolymer resin or maleic anhydride grafted product of ethylene-α-olefin copolymer (d) Heat Silicone modified product obtained by graft-polymerizing a reactive polyorganosiloxane on a plastic resin (e) Hydrated metal compound The olefin resin used by silane-grafting in the present invention includes low density polyethylene, medium density polyethylene and high density polyethylene. Density polyethylene, ethylene and α-o Copolymers of fins, ethylene-vinyl acetate copolymer resin (EV
A), ethylene ethyl acrylate copolymer resin (EEA),
Examples thereof include ethylene methyl methacrylate copolymer resin (EMMA), ethylene propylene rubber, and ethylene propylene diene rubber. The α-olefin of the copolymer of ethylene and α-olefin used in the components (a), (b) and (c) is C _{3 to} C ₁₂ such as propylene and 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, dodecene-1 and the like.
Particularly preferred are butene-1, pentene-1,
Hexane-1, heptene-1, and 4-methylpentene-1 can be mentioned. The silane graftmer of the component (b) used in the present invention is obtained by adding the above-mentioned olefin resin to the general formula RR'SiY ₂ (R
Is a monovalent olefinic unsaturated hydrocarbon group, Y is a hydrolyzable organic group, R'is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon or an organic silane represented by Y). It is obtained by reacting under a free radical-forming compound. This uses a known method disclosed in JP-B-57-24373 and JP-B-48-1711, and JP-A-50-24342. Specifically, for example,
It is obtained by using vinyltrimethoxysilane and the like in combination with an organic peroxide having a strong polymerization initiation action such as dicumyl peroxide (DCP) based on a polyolefin resin. The amount of silane graftmer, in 100 parts by weight of the resin,
It is preferably 2% by weight or more, and if it is less than this, the effect of retaining shape at high temperature and preventing dripping during combustion is small. The degree of cross-linking of the silane graftmer is the gel fraction as xylene-insoluble residual fraction.
20% to 80% by weight is preferred. If the gel fraction is less than 20% by weight, shape retention at high temperatures and sagging prevention effect at the time of burning are weak, and if the gel fraction exceeds 80% by weight, moldability becomes poor. Component (c) used in the present invention is a maleic anhydride grafted product of polyethylene, a maleic anhydride grafted product of ethylene-vinyl acetate copolymer resin, or ethylene-.
The amount of the maleic anhydride grafted product of the α-olefin copolymer is less than 0.1 parts by weight, the effect is small, and
If the amount is more than parts by weight, the bond due to the reaction with the hydrated metal compound is too strong and the extrudability and the appearance during extrusion are deteriorated. Therefore, the amount of component (c) added is 100 for component (a) + component (b).
0.1 to 30 parts by weight is preferable with respect to parts by weight. The thermoplastic resin used in the silicone modified product obtained by graft-polymerizing the reactive polyorganosiloxane of the component (d) of the present invention includes polyethylene, polypropylene, a copolymer of ethylene and α-olefin, EVA, E
Examples thereof include polyolefin resins such as EA and EMMA, polystyrene, and acrylonitrile-butadiene-styrene copolymer resins. Examples of the reactive polyorganosiloxane include the following silicone gums. I.e. In addition, EMMA, PS, and HDPE obtained by reacting the above with SP-100, SP-200, SP manufactured by Dow Corning Co., Ltd.
-300 and so on. When the amount of the silicone modified product added is less than 0.1 parts by weight, the effect is weak, and when it exceeds 30 parts by weight, no remarkable effect exceeding the improvement effect of the present invention is exhibited and the product becomes expensive, which is not practical. Therefore, the amount of component (c) added is (a)
It is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the + (b) component. As the hydrated metal compound of the component (e) used in the present invention, a hydrated metal compound having a decomposition initiation temperature of 150 ° C to 4 ° C is used.
Represented by the general formula MmOn · XH ₂ O in the range of 50 ° C. (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 indicating bound water) A compound or a double salt containing the compound, and specifically, for example, 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 [C
aO ・ H ₂ O or Ca (OH) ₂ ], barium hydroxide [BaO ・ H ₂ O or
BaO ・ 9H ₂ O], zirconium oxide hydrate [ZrO ・ nH ₂ O],
Tin oxide hydrate [SnO · H ₂ O], basic magnesium carbonate [3MgCO ₃ · Mg (OH) ₂ 3H ₂ O], hydrotalcite [6MgO
・ Al ₂ O ₃・ H ₂ O], dawsonite [NaCO 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] and the like. If the amount added is less than 50 parts by weight, it is difficult to obtain the desired flame retardant effect, and if it exceeds 300 parts by weight, mechanical properties such as tensile strength are deteriorated and extrusion processability is deteriorated. If desired, the flame-retardant olefin resin composition of the present invention may contain other commonly used additives. Examples of the additive include an antioxidant, a neutralizing agent, an ultraviolet absorber, an antistatic agent, a pigment, a dispersant, a lubricant, a thickener, a foaming agent, a metal deterioration preventing agent, an antimold agent, a flow control agent, There are flame retardants of phosphorus or phosphine derivatives, other inorganic fillers, crosslinking agents or crosslinking aids. It is also possible to crosslink by electron beam irradiation. The method for producing the flame-retardant olefin resin composition of the present invention includes (a) a copolymer of ethylene and α-olefin, an ethylene-ethyl acrylate copolymer resin, or an ethylene-methyl methacrylate copolymer resin. (B) Silane graft mer of olefin resin pre-silane-grafted (c) Polyethylene maleic anhydride graft product, ethylene-vinyl acetate copolymer resin maleic anhydride graft product or ethylene Maleic anhydride grafted product of -α-olefin copolymer (d) Silicone modified product obtained by graft-polymerizing reactive polyorganosiloxane on thermoplastic resin (e) Hydrated metal compound (i) (a) When (b), (c), (d) and (e) are produced by batch kneading, (ii) Silang of (b) At the time of Tomah created (c)
When one or more kinds of (d) are added to prepare a pellet-form silane graftmer, and then (a) and (e) are added for kneading production (iii) (a) (b) (c) ) (D) (e), an arbitrary component is selected, kneaded in advance, and then kneaded with the remaining components to produce a mixture. The flame-retardant olefin resin composition of the present invention exhibits a combustion suppression effect which is completely different from the combustion suppression effect of the conventional carbon powder-added flame-retardant resin composition, and facilitates identification according to the purpose. Therefore, even if various pigments are added, the combustion suppressing effect does not change, so that coloring can be freely performed according to the application.

【Example】

Examples will be described below. (Study Example 1) First, a polyolefin-based resin having the composition shown in Table 1 was prepared according to the following procedure. Dicumyl peroxide (DCP) is dissolved in vinyltrimethoxysilane (VTMOS), and ultra low density polyethylene (V
LDPE) (1), ethylene ethyl acrylate copolymer resin (EEA) (2) and low density polyethylene (3) are used, and the ones according to the formulation in Table 1 are mixed and stirred, and this is a uniaxial 50 mmφ. Extrusion was carried out at an extrusion temperature of 150 to 200 ° C. using an extruder to obtain silane-grafted silane graft mer resins A, B and C in the form of pellets. Resins A, B, and C were each hermetically sealed in an aluminum laminate bag, stored in a state where external moisture was blocked, and dispensed as needed for use. Next, the various components shown in Table 2 are mixed together in a container,
It was kneaded and granulated with a Banbury roll. The obtained composition was again subjected to roll pressing to prepare various measurement test pieces. Using this test piece, it was immersed in water, carbon dioxide gas was blown into it, and the degree of whitening of the surface due to the formation of magnesium carbonate and the weight change due to 10% sulfuric acid and 3% caustic soda were measured, and the surface was not scratched or bent. Oxygen index is measured as whitening and flame retardancy, and as workability, the outer diameter is 20mmφ and inner diameter is 18 depending on the extruder.
A tube with mmφ and a thickness of 1 mm was extruded, the extrudability was evaluated, and the buckling using this extruded tube was also evaluated. As a result, as can be seen from the examples shown in Table 2, the flame-retardant olefin resin composition of the present invention has a whitening degree, chemical resistance to chemical resistance by sulfuric acid and caustic soda, surface scratches, and a surface upon bending. It can be seen that the whitening buckling is significantly improved. The raw materials used in the study example are as follows. Note: (1) Ultra-low density polyethylene (VLDPE) [Japan Petrochemical Co., Ltd. Softlex D9052] (2) Ethylene ethyl acrylate copolymer resin (EEA) [Japan Petrochemical Co., Ltd. Lexron A2150] (3) Low density polyethylene (LDPE) [C215 manufactured by Sumitomo Chemical Co., Ltd.] (4) Ethylene methyl methacrylate (EMMA) [CM1004 manufactured by Sumitomo Chemical Co., Ltd.] (5) Maleic anhydride grafted polyolefin [Mitsui Petrochemical Co., Ltd. ) MFR1.3, density 0.94 ethylene-α-olefin copolymer base] (6) Maleic anhydride grafted polyolefin [Nippon Petrochemical Co., Ltd. MFR0.3, density 0.92 ethylene-α
-Olefin copolymer base] (7) Silicone modified product [Dow Corning Co., Ltd. silicone content 40 wt% low density polyethylene base] (8) Aluminum hydroxide [Showa Denko KK Hijilite H42M] (9) Magnesium hydroxide [Kyowa Chemical Co., Ltd., Kimas 5B] (10) Lubricants / stabilizers (combined below) Sanyo Kasei Co., Ltd. Sun Wax 171P 1.0 parts by weight Ciba Geigy Co., Ltd. Irganox 1076 0.3 parts by weight Sumitomo Chemical Industry Co., Ltd. Sumilizer WXR 0.3 parts by weight (11) Pigment Black: VALCAN 9A-32 3.0 parts by weight (12) Distilled water Exchanged water 1 with a 5 cm x 5 cm x 1 mmt press sheet immersed in it. Blowing 100 ml / min of carbon dioxide gas 48
After a lapse of time, it was taken out, and the degree of whitening (magnesium carbonate crystal formation) was visually observed. (13) Weight change measurement by immersion in 10% sulfuric acid (50 ° C x 7 days) Test piece shape: JIS No. 3 dumbbell used 1mmt (14) Weight change measurement by immersion in 3% caustic soda (50 ° C x 7 days) Test piece shape: JIS3 No. dumbbell used 1mmt (15) Pencil HB hardness: visual judgment by scratching (16) 2mm thick sheet 180 degree bending whitening visual test (17) JIS K 7201 (18) outer diameter 20mmφ, inner diameter 18mmφ, thickness 1mm, long Prepare a test sample in which an electric wire [a body single wire with a conductor diameter of 1 mmφ and a soft vinyl chloride composition with a hardness (JIS A) of 80 and a thickness of 8 mm is inserted] was inserted into a 300 mm extruded tube. Diameter
The occurrence of wrinkles when bent along a 100 mmφ mandrel was visually determined. (19) Using 50mmφ single screw extruder (150-160-170-180 ° C,
L / D25, CR3.5) Extrusion processability of a tube with an inner diameter of 15 mmφ and an outer diameter of 18 mmφ was evaluated. Evaluation method: The order was excellent>good>acceptable> not acceptable, and the grades of acceptable were acceptable.

【The invention's effect】

When the flame-retardant olefin-based resin composition of the present invention is molded, (1) the silane graftmer does not require any help of a catalyst for accelerating the crosslinking, and the hydroxy group (OH group) on the surface of the hydrated metal compound is used. And silane grafter silanol groups Due to the influence of a slight amount of water on the surface of the hydrated metal compound and the hydrated metal compound similar to the catalyst of the organometallic compound, a condensation reaction due to hydrolysis occurs under the environment of frictional heat generated during kneading, and a strong siloxane bond (- Si-O-MmOn; M is a metal). (2) A maleic anhydride grafted product of polyethylene, a maleic anhydride grafted product of an ethylene-vinyl acetate copolymer resin or a maleic anhydride grafted product of an ethylene-α-olefin copolymer, which is the component (c), and the component (e). Reacts with the metal ions of the hydrated metal compound to form a complex salt, showing a remarkable effect. (3) The silicone modified product contributes to improvement of wear resistance and moldability of the composition. As described above, due to the synergistic effect of the siloxane bond between the silane graftmer and the hydrated metal compound and the bond due to the formation of a complex salt between the maleic anhydride derivative of the component (c) and the hydrated metal compound, and the effect of the silicone modified product. The surface deterioration of the flame-retardant olefin resin composition, the reduction in chemical resistance, the surface scratches, the whitening of the surface during bending, and the buckling were significantly improved.

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Claims (1)

[Claims] 1. A composition comprising the following components (a) to (e), wherein 0.1 to 30 parts by weight of (c) and (d) are added to 100 parts by weight of (a) + (b). ) 0.1 to 30 parts by weight and (e) 50 to 300 parts by weight, a flame-retardant olefin 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) Silane grafted in advance Silane grafter of olefin resin (c) Maleic anhydride grafted product of polyethylene, maleic anhydride grafted product of ethylene-vinyl acetate copolymer resin or maleic anhydride grafted product of ethylene-α-olefin copolymer (d) Heat Silicone modified product obtained by graft-polymerizing a reactive polyorganosiloxane on a plastic resin (e) Hydrated metal compound