JPH06207048A - Flame-retardant composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. which is excellent in flame retardance, moldability, molding appearance. and rubber elasticity and suitable for solid or foam molding with or without cross-linking by compounding 1,2-polybutadiene with a specified amt. of a metal hydroxide. CONSTITUTION:The compsn. is obtd. by compounding 100 pts.wt. compsn. comprising 10-100wt.% 1,2-polybutadiene and 90-0wt.% at least one polymer selected from the group consisting of a diene rubber, a block copolymer of an arom. vinyl compd. with a conjugated diene, and an ethylene-vinyl acetate copolymer (e.g. a natural rubber) with 5-100 pts.wt. metal hydroxide (e.g. aluminum hydroxide). Pref. 100 pts.wt. compsn. thus obtd. is further compounded with 1-70 pts.wt. organohalogen and/or organophosphorus compd. (e.g. decabromodiphenyl oxide) and 1-30 pts.wt. Sb compd. (e.g. Sb2O3).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant composition suitable for soft OA / electrical parts, industrial parts and automobile parts which are excellent in flame retardancy, moldability, molding appearance and rubber elasticity.

[0002]

2. Description of the Related Art 1,2-Polybutadiene exhibits flame retardant properties such as excellent moldability, molding appearance, rubber elasticity, and softness, but 1,2-polybutadiene itself has an essentially hydrocarbon structure. Because it is flammable, it is difficult to make it flame-retardant even if organic halogen compounds, organic phosphorus compounds, and antimony compounds, which are commonly used as flame retardants for plastics and rubbers, are added. No results have been obtained.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention is excellent in flame retardancy, rubber elasticity, softness, molding appearance and moldability, and is suitable for non-crosslinking molding, crosslinking molding, solid molding and foam molding. The purpose is to provide things.

[0004]

The present inventors have found that a flame-retardant composition that achieves the above-mentioned object can be obtained by mixing a specific elastomer with a metal hydroxide, and have reached the present invention. . That is, the present invention provides (A) 1,2-
10 to 100% by weight of polybutadiene and 0 to 90% by weight of at least one member selected from the group consisting of (B) diene rubber, block copolymer of vinyl aromatic compound and conjugated diolefin, ethylene-vinyl acetate copolymer. Ingredient 1
To 100 parts by weight of the flame-retardant composition obtained by adding 5 to 100 parts by weight of the (C) metal hydroxide to 00 parts by weight, and (100 parts by weight of the flame-retardant composition according to claim 1), D) 1 to 7 organic halogen compounds and / or organic phosphorus compounds
A flame-retardant composition comprising 0 part by weight and 1 to 30 parts by weight of (E) an antimony compound.

The present invention will be described in detail below. 1,2-polybutadiene which is the component (A) of the present invention is
1,2-bond 70% or more, preferably 80% or more, crystallinity 5-40%, preferably 10-35%, [η]
Is 0.5 dl / g or more, preferably 0.6 dl / g or more. Examples of the diene rubber that is the component (B) of the present invention include butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SB
R) and acrylonitrile-butadiene rubber (NBR). Of these, NR, IR and SBR are preferable. Aromatic vinyl compound which is the component (B) of the present invention
As the conjugated diene block copolymer, at least one polymer block of an aromatic vinyl compound and at least 1
It includes one conjugated diene compound polymer block, and may be a linear type or a radial type.
Further, the conjugated diene block may be a random copolymer with a small amount of an aromatic vinyl compound, or may be a so-called tapered block in which the aromatic vinyl compound content gradually increases.

The structure of the block copolymer is not particularly limited, and any of (ab) n type, (ab) na type and (ab) nc type can be used. Where a
Is a polymer block of an aromatic vinyl compound, b is a conjugated diene polymer block, c is a coupling agent residue, and n is an integer of 1 or more. In the above block copolymer, it is of course possible to use a block copolymer having a conjugated diene moiety hydrogenated.

The aromatic vinyl compound of the aromatic vinyl compound-conjugated diene block copolymer used in the present invention is styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, or Although vinyl naphthalene or the like is used, styrene is particularly preferable. As the conjugated diene, 1,3-butadiene, isoprene, piperylene and the like are used, and among them, 1,3-butadiene and isoprene are particularly preferable. The weight average molecular weight of the block copolymer is 10,
It is preferably 000 to 800,000, more preferably 50,000 to 500,000. The content of aromatic vinyl compound in the block copolymer is preferably 5 to 60% by weight, more preferably 20 to 50% by weight.

The ethylene-vinyl acetate copolymer which is the component (B) of the present invention has an acetic acid content of 5 to 40% by weight, preferably 10 to 20% by weight and a melt index of 1 to 40 g /
10 min (190 ° C, 2160 g), preferably 10
It is 30 g / 10 min (190 ° C., 2160 g). Ratio (A) / (B) of the present invention
(B) is 10 to 100% by weight / 0 to 90% by weight, preferably 30 to 100% by weight / 0 to 70% by weight, and more preferably 60 to 100% by weight / 0 to 40% by weight.
When the content of 1,2-polybutadiene is less than 10% by weight, fluidity (moldability) and molding appearance are deteriorated, which is not preferable.

Examples of the metal hydroxide as the component (C) of the present invention include group II and group III metal hydroxides such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and calcium hydroxide. Of these, the preferred metal hydroxide is aluminum hydroxide. The aluminum hydroxide preferably has an average particle size of 0.5 to 70 μm. The flame retardant mechanism of metal hydroxide is such that the water of crystallization contained in the chemical structure is released at high temperature, absorbs a large amount of heat, and prevents ignition and combustion. When the metal hydroxide is used in the present invention, in addition to the above-mentioned effects, excellent electrical characteristics, mechanical characteristics, heat resistance, and weather resistance are imparted.

The addition amount of the metal hydroxide which is the component (C) of the present invention is 10 in total of the components (A) and (B) of the present invention.
5 to 100 parts by weight, preferably 10 to 8 parts by weight
The amount is 0 parts by weight, more preferably 30 to 80 parts by weight.
When the amount of the metal hydroxide added is less than 5 parts by weight, flame retardancy is impaired, which is not preferable, and when it exceeds 100 parts by weight, moldability and appearance are impaired, which is not preferable.

Examples of the organic halogen compound and the organic phosphorus compound as the component (D) of the present invention include halogenated phosphates such as tris (chloroethyl) phosphate and tris (monochloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene. Diphosphate glycidyl-α-methyl-β-di (butoxy) phosphinyl-propionate, phosphoric acid esters such as dibutylhydroxymethylphosphonate, di (butoxy) phosphinyl-propylamide, dimethylmethylphosphonate, ethylene-bis-tris ( 2-Cyanoethyl) phosphonium-bromide, di- (polyoxyethylene)-
Hydroxymethylphosphonate, phosphorus-chlorine containing oligomer, ammonium polyphosphate, butylpyrophosphate, butyl acid phosphate, butoxyethyl acid phosphate, melamine phosphate, phosphorus-chlorine flame retardant, red phosphorus flame retardant, chlorinated paraffin , Chlorinated polyolefin, chlorinated polyethylene, perchlorocyclopentadecane, hexabromobenzene, decabromodiphenyl oxide, polydibromophenylene oxide, bis (tribromophenoxy) ethane, ethylene-bis-
Dibromonorbornenecarboximide, ethylene-bis-tetrabromophthalimide, tetrabromo-bisphenol A derivative, bis (tribromophenoxy) ethane, dibromoethyl-dibromocyclohexane, dibromoneopentyl glycol, tribromophenol, tribromophenyl allyl ether, tetrabromo- Bisphenol S, tetradecabromo-diphenoxybenzene, tris (2,3-dibromopropyl-1-) isocyanurate, 2,2-bis (4-hydroxy-3,5)
-Dibromophenyl) propane, pentabromophenol, pentabromotoluene, pentabromodiphenyl oxide, hexabromocyclododecane, hexabromodiphenyl ether, octabromodiphenyl oxide,
Examples thereof include N-methylhexabromodiphenylamine, aromatic bromine compounds, brominated epoxy resins, brominated polystyrene, and other brominated flame retardants. Of these, brominated compounds are particularly preferable.

The component (D) of the present invention is an organic halogen compound and / or an organic phosphorus compound, and when the component (E) is added, a further excellent flame retardancy can be obtained. The preferable addition amount of the component (D) is the component (A) + (B) = 1 of the present invention.
1 to 70 parts by weight, more preferably 1 to 100 parts by weight
It is 0 to 60 parts by weight, particularly preferably 20 to 50 parts by weight. When it is less than 1 part by weight, the effect of adding the component (D) cannot be obtained, while when it exceeds 70 parts by weight, rubber elasticity, molding processability and molding appearance are deteriorated, which is not preferable. Examples of the antimony-based compound that is the component (E) of the present invention include antimony trioxide, antimony pentoxide, sodium antimonate, and the like. Of these, antimony trioxide is particularly preferable. When the antimony-based compound which is the component (E) of the present invention is added, more excellent flame retardancy is obtained, and the addition amount of the component (D) is 100 parts by weight of the component (A) + (B) of the present invention. Preferably 1 to 30 parts by weight, more preferably 2 to
20 parts by weight, particularly preferably 5 to 15 parts by weight. 1
If it is less than 30 parts by weight, the effect of adding the component (E) cannot be obtained, and if it exceeds 30 parts by weight, rubber elasticity, moldability and molding appearance are impaired, which is not preferable.

As a stabilizer for the flame-retardant composition of the present invention, it is preferable to add a phosphite, an epoxy compound, or an organic tin compound because the thermal stability during molding is improved.
With respect to moldability, it is preferable to add a small amount of hydrogenated hydrogenated castor oil or low molecular weight polyethylene silicone oil, which is preferable. If desired, various additives can be added to the composition of the present invention. Examples of the inorganic filler include talc, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid, titanium oxide, glass fiber, carbon fiber, cotton floc and various carbon blacks. As the softening agent, for example, process oil, lubricating oil,
Paraffin, liquid paraffin, petroleum asphalt, petroleum softeners such as petrolatum, coal tar softeners such as coal tar and coal tar pitch, linseed oil, rapeseed oil, coconut oil and other fatty oil softeners, tall oil, sub Oils and waxes such as beeswax, carnauba wax and lanolin, ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, fatty acids and fatty acid salts such as zinc lanolate, and synthetic polymer substances such as petroleum resin. To be Examples of the plasticizer include phthalic acid ester-based, adipic acid ester-based, sebacic acid ester-based, and phosphoric acid-based resins. Examples of the tackifier include coumarone indene resin, terpene-phenol resin, xylene-formalin resin and the like.
As the colorant, inorganic and organic pigments, and as the foaming agent, for example, sodium bicarbonate, ammonium carbonate,
N, N'-dinitrosopentamethylenetetramine, azocarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, toluenesulfonylhydrazide, calcium amide, paratoluenesulfonylamide, and the like, examples of the foaming aid include salicylic acid and phthalic acid. , Urea and the like. As the resin, the melting point is 1
The resin is not particularly limited as long as it is a resin of 80 ° C. or lower. As the vulcanizing agent, sulfur, dipentamethylene thiuram, sulfur compounds such as tetrasulfide, dicumyl peroxide, 1,1′-di- (t-butylperoxy)
-3,3,5-trimethyldichlorohexane, di- (t-
Butylperoxy) diisopropylbenzene, 2,5-
Peroxides such as dimethyl-2,5-di- (t-butylperoxy) hexane, P-quinonedioxime, P,
An oxime compound such as P′-dibenzoylquinone dioxime can be used alone or in combination. The mixing method for producing the composition of the present invention is not particularly limited, a normal resin, a roll used during rubber processing,
Mixing and kneading can be performed using a kneader, Banbury mixer, screw extruder, feeder-ruder extruder, tumbler, Henschel mixer. The composition of the present invention thus obtained is suitable for soft OA / electrical parts excellent in flame retardant rubber elasticity, industrial parts, automobile parts and building parts, and is non-crosslinking molded, crosslinked molded and foamed, non-crosslinked It can be used in a wide range of processing means such as in the foaming field.

[0014]

[Judgment]

◯: 1/8 inch thick × 50 inch × 1/2 inch, the burning rate in the 3 inch section of the sample does not exceed 1.5 inch per minute. X: Same as above Samples and conditions Over 1.5 inches. (2) Softness with excellent rubber elasticity (hardness method) Measured with Shore D type spring hardness [Judgment] ○: 60 or less ×: 60 or more

(3) Molding appearance Non-cross-linking system <Molding conditions> Molding machine: 10 ounce in-line screw type injection molding machine Mold: 1/8 inch thickness x 50 inch x 1/2 inch side gate plate Molding temperature: 150 ° C Injection pressure: 660kg / cm ² Flow control: Medium loading: 8 seconds Injection: 10 seconds Curing: 30 seconds Mold temperature: 30 ° C Evaluation: Flow mark on the surface of molded product, rough skin, brushing, silver streak, blooming Etc. were visually evaluated. [Judgment] ○: Excellent △: Usable ×: Not usable Crosslinking system molding machine: 145TON steam press Mold: 1/8 inch thickness x 50 inch x 1/2 inch Mold for molding Crosslinking condition: 160 ° C x 10 minutes Evaluation : Color unevenness, rough skin, blooming [Judgment] ○: Excellent △: Usable ×: Not usable (4) Molding processability (fluidity) Non-crosslinking type fluidity is 4 × 4 × 1000 mm fan gate spiral mold. It was used and molded under the following molding conditions. 150 ° C
Determine the flow length (mm) of the resin flowing in the spiral cavity at the molding temperature.

[0016] [Evaluation] ○: 50mm or more ×: evaluated at 50mm below (5) crosslinking crosslinking molding appearance evaluation when the crosslinking. [Judgment] ◯: Crosslinking was good x: Crosslinking was poor (6) Foamability The expansion ratio (volume ratio) was evaluated. [Judgment] ○: 1.5 times or more ×: Less than 1.5 times

[Details of Materials Described in Examples] 1) RB820 1,2-polybutadiene, crystallinity 25.5%, manufactured by Nippon Synthetic Rubber Co., Ltd. 2) TR1000 aromatic vinyl compound-conjugated diene block copolymer, Bonded styrene 40%, manufactured by Japan Synthetic Rubber Co., Ltd. 3) UE633 ethylene vinyl acetate copolymer, vinyl acetate content 20%,
MI (190 ° C, 2160g) 20%, manufactured by Tosoh Corporation 4) Heidilite H-30 aluminum hydroxide, specific gravity 2.4, average particle size 3 to 20
μ, Showa Denko KK 5) Kisuma 5 magnesium hydroxide, apparent specific gravity of 0.69 to 0.56,
Crystal grain size 0.6 to 0.8 μm, manufactured by Kyowa Chemical Co., Ltd. 6) AFR-1021 decabromodiphenyl oxide, melting point 285 ° C., bromine content 81 to 83%, manufactured by Asahi Glass Co., Ltd.

7) FCP # 100 antimony trioxide, specific gravity 4.0, particle size 250 mesh all through, manufactured by Kawashige Co., Ltd. Examples 1, 2, 3, 6, 8 Examples 1 and 2 shown in Table 1 and Table 2, 2, 3, 6 and 8 are claimed compositions in non-crosslinked molding (Example 6 is a foam system). That is, the processing was performed by kneading the compositional components shown in Tables 1 and 2 with a pressure kneader, making a sheet with a roll machine, pelletizing the sheet with a sheet pelletizer, and injection molding. The evaluation results are shown in Tables 1 and 2. Examples 4, 5 and 7 Examples 4, 5 and 7 shown in Table 1 and Table 2 are claimed compositions in cross-linking molding (Example 4 is a foaming system). That is, the processing was carried out by kneading the compositional components shown in Tables 1 and 2 at 70 to 120 ° C. using a pressure kneader and a roll machine, and putting the sheeted product into a predetermined mold under the conditions of 160 ° C. and 10 minutes. Was press-molded. The evaluation results are shown in Tables 1 and 2. Comparative Examples 1 to 3 Comparative Examples 1 to 3 shown in Table 1 and Table 2 are compositions outside the scope of the claims. The kneading process, the molding process, and the evaluation are performed in Example 1.
Same as. As is clear from Tables 1 and 2, the compositions of the present invention (Examples 1 to 8) are significantly superior in flame retardance to the compositions (Comparative Examples 1 to 3) that are outside the range of the composition of the present invention. sex,
It is an epoch-making composition that exhibits flexibility, molding processability, and molding appearance and cannot be manufactured by conventional techniques.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

The composition of the present invention has a highly balanced flame retardancy, softness, moldability, and molding appearance that have hitherto been unobtainable. The composition of the present invention makes use of the above-mentioned excellent patents, and uses foot rubber, packing and other OA equipment, home appliances, industrial products, engine room parts, automobile materials such as interior materials, kitchen parts, building products such as wiring surroundings, and civil engineering products. It can be suitably used for applications such as, cushioning materials, and packaging materials, and can be useful over a wide range of applications, and its industrial utility value is extremely high.

 ─────────────────────────────────────────────────── --Continued front page (72) Inventor Isao Miyaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. (A) 1,2-polybutadiene 10 to 1
And (B) a diene rubber, a block copolymer of a vinyl aromatic compound and a conjugated diolefin, and at least one component selected from the group consisting of ethylene-vinyl acetate copolymers in an amount of 0 to 90% by weight. A flame-retardant composition obtained by adding 5 to 100 parts by weight of (C) metal hydroxide to 100 parts by weight. 2. 1 to 70 parts by weight of (D) an organic halogen-based compound and / or an organic phosphorus-based compound, and (E) based on 100 parts by weight of the flame-retardant composition according to claim 1).
A flame-retardant composition comprising 1 to 30 parts by weight of an antimony compound.