JPH0788443B2 - Flame-retardant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition.

2. Description of the Related Art Conventionally known flame-retardant resin compositions include halogen-containing polymers or non-halogen-based polymers to which an organic halogen-based flame retardant is added. However, products obtained by using such a flame-retardant resin composition all self-extinguish when they are moved away from the flame, but when they are in a high-temperature flame such as a fire, they burn to the end. However, there are drawbacks such as a large amount of smoke being generated, and thermal decomposition causing the generation of corrosive and highly toxic acid gas.

OBJECT OF THE INVENTION The present invention is halogen-free and has excellent flame retardancy, mechanical strength, electrical characteristics, aging resistance, does not generate corrosive or toxic acid gas even when exposed to flame, and does not emit smoke. It is an object of the present invention to provide a flame-retardant resin composition having properties such as low content.

Structure of the Invention That is, the present invention, the olefin resin 100 parts by weight, hydrated alumina and / or hydrated magnesia 50 to 250 parts by weight, Ni, M
It relates to a flame-retardant resin composition comprising 0.1 to 8 parts by weight of an oxide of a metal selected from n and Zr and 3 to 50 parts by weight of carbon black.

As the olefin resin used as the base polymer in the present invention, conventionally known ones can be widely used, for example, olefin homopolymers such as polyethylene, polypropylene and polystyrene, ethylene-propylene rubber (EP
M), olefin copolymers such as ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SB
R), isobutylene-isoprene rubber (IIR), acrylonitrile-butadiene rubber (NBR), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), etc. Examples thereof include polymers.

Among these, an essentially linear polyethylene obtained by polymerizing ethylene under low pressure using a catalyst having 4 to 10 carbon atoms as a comonomer and having a density of 0.91 to
Those having a range of 0.96 and a melt index (MI) of 0.1 to 10 are preferred. Examples include Yucaron LL and F-30
F, F-30H (both manufactured by Mitsubishi Petrochemical Co., Ltd.), Ultox 25
20L, 3520F, 3021F (all manufactured by Mitsui Petrochemical Co., Ltd.), DFD
Examples include A-7540 (made by Union Carbide) and the like.

Another preferred olefin resin is a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, which is polymerized with a Ziegler catalyst, and has MI of 1 to 10 and density of 0.85 to 0.
The range of 90 can be illustrated. Examples thereof include Tuffmer A-4090, A-4085, P-0180, P-0480 (all manufactured by Mitsui Petrochemical Co., Ltd.).

Other preferred olefin resin is a copolymer of ethylene and propylene having a propylene content of 15 to 70 mol%, preferably 20 to 50 mol%, and the above ethylene and propylene. An ethylene-propylene-diene terpolymer obtained by copolymerizing dichloropentadiene (DCPD), ethylidene norbornene (ENB), 1,4-hexadiene (1,4HD), etc. as the third component The amount of the third component is 8 to 25, preferably 9 to 15, and the raw rubber Mooney viscosity is in the range of 30 to 70. Examples of the resin, EP21, EP51
[All made by Japan Synthetic Rubber Co., Ltd.], Esplen 301, Esplen 501 [all made by Sumitomo Chemical Co., Ltd.], EPT4021, EPT104
5 (all manufactured by Mitsui Petrochemical Co., Ltd.) and the like are included.

Still another preferred olefin resin is a copolymer of ethylene and vinyl acetate having a vinyl acetate content of 2 to 50.
Those having a weight percentage and MI of 1 to 30 are included. Examples thereof include Levapren 450, Levapren 452 (all manufactured by Bayer), Evatate-D2021, H2031, K2010 (all manufactured by Sumitomo Chemical Co., Ltd.), NUC8450, 3145 (all manufactured by Nippon Unicar).

In the present invention, the olefin resin may be used singly or as a mixture (blend) of two or more. The olefin resin may be crosslinked. As the crosslinked olefin resin, widely known ones can be widely used. Specifically, the above olefin resin is added with an organic peroxide, and heat-treated to crosslink the olefin resin with an electron beam. Examples of the resin include those obtained by irradiating the above with a crosslinked olefin resin and those obtained by crosslinking a water-crosslinkable olefin resin.

In the composition of the present invention, hydrated alumina and /
Alternatively, it is necessary to incorporate hydrated magnesia. As the hydrated alumina used in the present invention, conventionally known ones can be widely used, for example, Al ₂ O ₃ .nH ₂ O (n shows 2.5 to 3.5), and more specifically, Hydilite H42M [Showa Light metal Co., Ltd.], B1403, B1403-D-18 (all manufactured by Nippon Light Metal Co., Ltd.) and the like, and conventionally known hydrated magnesia can be widely used. For example, MgO.mH ₂ O (m is 1.5
.About.2.5) and the like. Among the above hydrated magnesia, those having a specific surface area of 3 to 15 m ² / g by the BET method and having a particle size distribution of 5 μm or more by the Rozetz method of 0% are particularly preferable. Specific examples thereof include Kisuma 5B, Kisuma 5A, Kisuma 5E (all manufactured by Kyowa Chemical Industry Co., Ltd.) and the like. In the present invention, such hydrated marmina and / or hydrated magnesia is usually added to polyolefin.
50 to 250 for 100 parts by weight (hereinafter simply referred to as "part")
Parts, preferably 70 to 200 parts, more preferably 80 to 150 parts. If the blended amount of hydrated alumina and / or hydrated magnesia exceeds 250 parts, the physical properties of the resulting composition deteriorate. Further, when the blending amount of hydrated alumina and / or hydrated magnesia is less than 50 parts,
Flame retardant performance will not be exhibited.

The feature of the present invention is that, in addition to the above hydrated alumina and / or hydrated magnesia, 0.1 to 100 parts by weight per 100 parts of polyolefin resin.
It is to add 8 parts, preferably 0.5 to 5 parts, of an oxide of a metal selected from Ni, Mn and Zr. Specific examples of such metal oxides include NiO, Ni ₂ O ₃ , MnO, and ZrO. These may be used alone or in combination of two or more. Since the metal oxide of the present invention can further improve the flame retardancy by its addition even in a relatively small amount as described above, it is possible to obtain the same flame retardancy as compared with the case where these are not added. The amount of hydrated alumina and / or hydrated magnesia required can be reduced, resulting in improved mechanical properties, electrical properties, etc. of the composition, or the same amount of hydrated alumina and / or hydrated With the addition amount of magnesia, it is possible to exert an effect that a higher flame retardancy can be imparted.

In the present invention, the red phosphorus content as a flame retardant aid is 80% or more, the loss on drying is 0.8% or less, the 74 mesh sieve residue is 7% or less, and the surface thereof is coated with a thermosetting resin. Red phosphorus may be added to the composition of the present invention. Here, examples of the thermosetting resin include a phenol resin and a phenol-formalin resin. Specific examples of such red phosphorus include Novalet # 120 and No Valet # 12uF [both manufactured by Rin Kagaku Kogyo].

In this case, such red phosphorus is usually added in an amount of 3 to 40 parts, preferably 5 to 15 parts, and more preferably 5 to 12 parts per 100 parts of the olefin resin. If the blending amount exceeds 40 parts, the physical properties of the obtained composition deteriorate. On the other hand, when the amount of the flame retardant auxiliary compounded is less than 3 parts, the flame retardant effect of the resulting composition becomes difficult to be exhibited.

Furthermore, in the composition of the present invention, the DBP oil absorption is 100 to 160 cm ^3.
A carbon black such as a furnace black whose ASTM code is recognized as N330 to N351 at / 100 g may be blended, and in this case, the flame retardancy of the resulting composition can be further improved. As such a carbon black, for example, those called HAF or HAF-HS carbon can be preferably exemplified, and specific examples thereof include, for example, diamond black H and diamond black HS (both manufactured by Mitsubishi Kasei Co., Ltd.),
Vulcan-3, Vulcan-3H (both manufactured by KYABOT CORPORATION), SEAST H, SEAST 3H (both manufactured by Tokai Electrode Co., Ltd.), Ketsu Embrack HAF (manufactured by Ketsutsu En), and the like. Among these, diamond black H and Vulcan-3 are particularly preferable.

In the present invention, such a carbon black is usually contained in an amount of 3 to 50 parts, preferably 5 to 20 parts, based on 100 parts of the olefin resin.
It is more preferable to add 5 to 15 parts. If the blending amount exceeds 50 parts, the resulting composition tends to harden and the mechanical properties tend to be impaired. On the contrary, if the amount of the flame retardant auxiliary compounded is less than 3 parts, the effect of addition disappears, which is not preferable.

In the composition of the present invention, a coupling agent can be blended if necessary. Alternatively, the hydrated alumina and / or the hydrated magnesia may be surface-treated in advance with a predetermined amount of coupling agent and used in the present invention. As the coupling agent, conventionally known ones can be widely used, and examples thereof include monoalkoxy type, neoalkoxy type, coordination type and chelate type titanate coupling agents and silane coupling agents. Among the above titanate coupling agents, those containing phosphorus are preferred. The coordination titanate coupling agent containing phosphorus is represented by the general formula (RO) ₄ Ti. [P (OR ') ₂ OH] ₂ [wherein R represents an alkyl group having 1 to 12 carbon atoms]. R'represents an alkyl group having 3 to 30 carbon atoms. ] Organic titanates represented by the following can be preferably exemplified. Specific examples thereof include tetraisopropyldi (dioctylphosphite) titanate [KR-41B, manufactured by Kenritsu Corporation], tetraoctyldi (ditridecylphosphite) titanate [KR-46B,
Manufactured by the same company] and the like.

The chelate-type titanate coupling agent has the general formula [In the formula, R represents an acyl group, a sulfonyl group, a phosphoryl group or an aryl group. X represents CH ₂ or C═O. ] Organic titanates represented by are preferable, specifically, diisostearoyloxyacetate titanate [KR-101, manufactured by Kenritsu Corporation], isostearoylmethacryloxyacetate titanate [KR-106, manufactured by the same company], isostearoyl acryloxy Examples thereof include acetate titanate [KR-110S, manufactured by the same company] and di (dioctylpyrophosphate) ethylene titanate [KR-238S, manufactured by the same company].

As the silane coupling agent, a trialkoxysilane having a carbon-carbon double bond or an epoxy group is preferable, and specifically, vinyl-tris (β-methoxyethoxysilane) [A172, manufactured by Nippon Unicar Co., Ltd.], γ-methacryl Roxypropyltrimethoxysilane [A174, manufactured by Nippon Unicar] can be exemplified.

In the present invention, such a coupling agent is usually used in an amount of 0.1 to 5 parts, preferably 0.2 to 3 parts, based on 100 parts of the olefin resin.
It is more preferable to add 0.3 to 1.5 parts. When the surface of hydrated alumina and / or hydrated magnesia is treated with the above-mentioned coupling agent, it is preferable to use the coupling agent in an amount so as not to deviate from the above range. By adding a coupling agent to the composition of the present invention, the mechanical strength of the composition obtained is improved and the processability is improved.

In addition to the above-mentioned various components, various known additives can be added to the composition of the present invention. Examples of such additives include naphthene-based, aroma-based, process oil, phthalic acid, esters, trimellitic acid, plasticizers such as epoxy resins, hindered phenols, aromatic amines,
Antioxidants such as thiopropionates, fillers such as mistron vapor talc, calcium carbonate and magnesium carbonate, pigments such as phthalocyanine blue, chrome yellow and red iron oxide, and lubricants such as stearic acid, oleic acid and higher fatty acid metal salts. Examples thereof include processing aids. The blending amount of these various additives can be appropriately determined within a wide range,
1 to 5 plasticizers per 100 parts of polyolefin resin
0 part, 0.1-10 parts antioxidant, 5-200 parts filler, 0.1-10 parts pigment, 0.1-5 parts lubricant, 0.1-10 parts processing aid
It is advisable to mix them in parts.

The composition of the present invention comprises tert-butylcumyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5 -Methods using organic peroxide cross-linking agents such as dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxy-isopropyl) benzene, electron beam or radiation You may crosslink by the irradiation crosslinking method etc. by etc. In that case, as the crosslinking aid, a crosslinking aid usually used in the above-mentioned crosslinking method may be used in combination. Preferred cross-linking aids include aliphatic or aromatic polyfunctional compounds, aliphatic polyfunctional cyclic compounds, nitrogen-containing polyfunctional cyclic compounds, metal-containing polyfunctional compounds, and especially nitrogen-containing polyfunctional compounds. Functional cyclic compounds, especially triallyl isocyanurate (TAIC),
Trimethallyl isocyanurate (TMAIC), triallyl cyanurate (TAC), triacryloyl hexahydro-1,3,5-triazine (TAF) and the like can be mentioned.

The amount of each of the crosslinking agent and the crosslinking aid used is 0.1 to 5 parts, preferably 0.3 parts, per 100 parts of the polyolefin resin.
~ 2 parts is recommended.

The composition of the present invention can be obtained by appropriately mixing the predetermined amounts of the above-mentioned various components and uniformly mixing them by a conventionally known method using a Banbury mixer, a Henschel mixer or the like. Further, in the polymer blend system, it is preferable that the polymer is first mixed uniformly and then the other components are mixed.

In using the composition of the present invention, various conventionally known molding methods can be widely adopted. For example, the composition of the present invention is kneaded using a kneader such as a roll kneader, and then this is used depending on the application. And may be formed into various shapes.

Effects of the Invention Since the composition of the present invention is halogen-free, a large amount of smoke is generated even when it is left in a flame at a high temperature such as in the case of fire, and a corrosive gas or It does not generate acid gas, and has excellent flame retardancy, mechanical strength, electrical characteristics, aging resistance and the like.
Therefore, the composition of the present invention is suitable as a coating material for building materials, pipes, hoses, sheets, sheet covers, wall materials, electric cables (internal insulators, outer sheaths, etc.).

Examples Hereinafter, examples will be given in order to explain the present invention in more detail.

The characteristics of the samples obtained in each example were tested by the following methods.

<Flame Retardancy Test> The composition of the present invention was uniformly kneaded using a roll mill, and then hot press molded to form a sheet sample having a thickness of 3.5 mm. According to JIS K 7201 (oxygen index method), this sample was prepared. Oxygen index (LOI) is calculated and flame retardancy is evaluated.

<Mechanical Properties> Sample sheets similar to those described above (Examples 1 to 11 and 13 to 16 described later)
And the composition of Comparative Examples 1 to 4 and 6 has a thickness of 1 mm.
2), and the properties of the compositions of Example 12 and Comparative Example 5) are examined by the following methods.

(1) 100% module (kg / mm ² ) According to ASTM D882.

(2) 200% module (kg / mm ² ) According to ASTM D882.

(3) Tensile strength (kg / mm ² ) According to ASTM D882.

(4) Elongation (%) According to ASTM D882.

Examples 1 to 16 and Comparative Examples 1 to 6 Predetermined amounts (parts by weight) of the respective components shown in Table 1 below were mixed by the following method to obtain compositions of the present invention. That is, the base polymer, the flame retardant, and the metal oxide were uniformly mixed with a roll mill to obtain a sheet-shaped composition. The conditions at this time are
For Examples 1-6 and Comparative Examples 1-2, 120-140 ° C,
100 to 130 ° C. for Examples 7 to 12 and Comparative Examples 3 to 4,
For Examples 13 to 16 and Comparative Examples 5 to 6, the temperature range was room temperature to 80 ° C.

Further, the above composition is 100-150 kg / c in a hot press, respectively.
A sheet of each composition was prepared by molding or molding and crosslinking under a pressure of m ² . The conditions at this time are as follows: Examples 1 to 6 and Comparative Example 1
No. 2 to 150 ° C. for 5 minutes, Examples 7 to 12 and Comparative Examples 3 to 4 at 170 ° C. for 45 minutes, and Examples 13 to 16 and Comparative Examples 5 to 6 at 165 ° C. for 30 minutes.

In Table 1, the symbols in each component are as follows.

<Base Polymer> A-1 ... Low-density polyethylene (Mitsui Petrochemical Co., Ltd., "Ultozex" 202DL, MI = 2.1, density = 0.920) A-2 ... Low-density polyethylene (Mitsubishi Yuka Co., Ltd., "Yukaron" LLF30F, MI = 1.0, density = 0.920) A-3 ... Ethylene vinyl acetate copolymer (Nippon Unicar Co., NUC8450, VA content = 15 wt%, MI = 2.0) A-4 ... Ethylene vinyl acetate copolymer (Sumitomo Chemical Co., Ltd. Made by
Evatate K2010, VA content = 25 wt%, MI = 3.0) A-5 ... Poly-α-olefin (Mitsui Petrochemical Co., Ltd., Tuffmer A4090, MI = 4.0, density 0.89) A-6 ... Poly-α-olefin (Mitsui Petrochemical Co., Tuffmer A0480, MI = 1.2, density 0.88) A-7 ... EPDM (Japan Synthetic Rubber Co., EP21, Mooney viscosity = 38, 3rd component = ENB, iodine value = 19) A-8 ... EVA (Bayer Co., Levaprene 450, VA content =
45wt%) <Flame retardant> B-1 ... Mg (OH) ₂ (Kyowa Chemical Co., Kisuma 5B) B-2 ... Al (OH) ₃ (Showa Light Metal Co., Ltd., Hijilite H42
M) <metal oxide> C-1 ... NiO (oxidized _{nickel) C-2 ... Ni 2 O} 3 ( sesquioxide nickel) C-3 ... MnO (manganese _{oxide) C-4 ... Al 2 O} 3 ( aluminum oxide) C-5 ... ZrO (zirconium _{oxide) C-6 ... Sb 2 O} 3 ( antimony oxide) C-7 ... FeO (iron _{oxide) C-8 ... Fe 2 O} 3 ( iron sesquioxide) <flame retardant assistant> D -1 ... Red phosphorus (Rin Kagaku Co., Novalet # 120) <Carbon black> E-1 ... HAF carbon (Mitsubishi Kasei Co., diamond black H) E-2 ... HAF carbon (Kyabot Vulcan-3) <Additives> F-1 ... Coordination type titanium coupling agent (Kenritch Co., KR41B, [Tetraisopropyldi (dioctylphosphite) titanate]) F-2 ... Coordination type titanium coupling agent (Kenritch Co., Ltd., KR46B, [Tetraoctyldi (ditridecylphosphite) titanium F-3 ... Chelate type titanium coupling agent (Kenritch Co., KR101, [Diisostearoyloxyacetate titanate)] F-4 ... Chelate type titanium coupling agent (Kenritch Co., KR201, [Diiso Stearoyl ethylene titanate]) F-5 ... silane coupling agent (manufactured by Nippon Unicar Co., A1)
72, [Vinyl-tris (β-methoxyethoxysilane)] F-6 ... Silane coupling agent (manufactured by Nippon Unicar Co., A1)
74, [γ-methacryloxypropyltrimethoxysilane]) F-7 ... Mistron vapor talc (magnesium silicate) F-8 ... Stearic acid F-9 ... Zinc stearate F-10 ... Zinc oxide F-11 ... Tri Allyl isocyanurate F-12 ... N, N'-m-phenylene bismaleimide F-13 ... Dicumyl peroxide F-14 ... Process oil (naphthene-based, manufactured by Nippon San Oil Co., Ltd.,
Sansen 4240, viscosity = 15 to 20 cst, specific gravity = 0.920) F-15 ... Mercaptobenzimidazole F-16 ... Anti-aging agent (Ouchi Shinko Co., Nocrac 300,
4,4'-dihydroxy-3,3'-di-tert-butyl-5,
5'-Dimethyl-diphenyl sulfaide) F-17 ... Irganox 1010 (manufactured by Ciba Geigy, tetrakis [methylene-3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate] methane) The respective properties of the molded sheet samples of the composition of the present invention obtained in each of the above examples are shown in Table 2 below.

From Table 2 above, it can be seen that the sheet obtained using the composition of the present invention has excellent properties, especially in terms of flame retardancy and mechanical properties.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display part (C08K 3/00 3:04 3:22) (56) References JP-A-53-92855 (JP , A) JP 54-28347 (JP, A) JP 61-225233 (JP, A) JP 59-221345 (JP, A)

Claims (1)

[Claims] 1. An olefin resin 100 parts by weight, hydrated alumina and / or hydrated magnesia 50 to 250 parts by weight, a metal oxide selected from Ni, Mn and Zr 0.1 to 8 parts by weight and carbon black 3 to 50. A flame-retardant resin composition, characterized by containing parts by weight.