JPH0155662B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a flame retardant resin composition. BACKGROUND ART Conventionally, flame-retardant resin compositions made by adding an organic halogen-based flame retardant to a halogen-containing polymer or a non-halogen-based polymer are known. However, although all products obtained using such flame-retardant resin compositions self-extinguish when kept away from flames, they do not burn to the end when exposed to high-temperature flames such as during a fire. If the process is continued, there are disadvantages such as smoke generation, highly corrosive and toxic acid gas generated by thermal decomposition, and resin melting and flowing. In addition, when used as a coating material for electric wires and cables, the resin composition has excellent ashing properties (the property of forming an ashing layer with excellent heat insulation effect when exposed to flame). That is required. The reason for this is that in the case of electric wire cables, if the ash layer is strong, it can act as a barrier against fire and prevent fire from entering the interior, and it also has an insulating effect, which protects the inside of the cable. become,
As a result, the communication function can be maintained using a communication line, and the power supply can be maintained using a power line. Means for Solving the Problems An object of the present invention is to provide a flame-retardant resin composition that can be suitably used as a coating material for electric wires and cables. Another object of the present invention is to provide a flame-retardant resin composition with excellent ashing properties. Another object of the present invention is to provide a flame-retardant resin composition that is halogen-free and has excellent flame retardancy, mechanical strength, electrical properties, aging resistance, etc. As a result of intensive research to develop such a flame-retardant resin composition, the present inventor found that a resin composition having the following specific composition has the desired properties of the present invention. The present invention was completed based on this knowledge. That is, in the present invention, 100 parts by weight of olefin resin,
Hydrated alumina and/or hydrated magnesia 50-300
3 to 40 parts by weight of red phosphorus with a red phosphorus content of 80% or more, a dry weight of 0.8% or less, a 74 mesh sieve residue of 7% or less, and whose surface is coated with a thermosetting resin. and DBP oil absorption of 100 to 160
cm ³ /100g and ASTM code is N330~N351
It relates to a flame retardant resin composition characterized in that it contains 3 to 50 parts by weight of furnace black recognized as . As the olefin resin used as the base polymer in the present invention, a wide variety of conventionally known ones can be used, such as polyethylene, polypropylene,
Olefin homopolymers such as polystyrene, olefin copolymers such as ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), isobutylene-isoprene rubber (IIR),
Acrylonitrile-butadiene rubber (NBR), ethylene-ethyl acrylate copolymer (EEA),
Examples include copolymers of vinyl monomers such as ethylene-vinyl acetate copolymers (EVA) and olefins. Among these, essentially linear low-density polyethylene obtained by polymerizing ethylene under low pressure using an olefin having 4 to 10 carbon atoms as a comonomer and a catalyst, with a density of 0.91 to 0.96 and a melt index of (MI) preferably in the range of 0.1 to 10.
Examples are Yucalon L-L, F-30F, F
-30H [all manufactured by Mitsubishi Yuka Co., Ltd.], Urtozex
2020L, 3520F, 3021F [all made by Mitsui Petrochemicals], DF-DA-7540 [made by Union Carbide]
etc. can be exemplified. Other preferred olefin resins include ethylene polymerized with a Ziegler catalyst and carbon atoms of 4 to 8.
An example is a copolymer with α-olefin having an MI of 1 to 10 and a density of 0.85 to 0.90. Examples include Tafmar A-4090, A-
Examples include 4085, P-0180, and P-0480 (all manufactured by Mitsui Petrochemicals). Other preferred olefin resins include:
A copolymer of ethylene and propylene, with a propylene content of 15 to 70 mol%, preferably 20 to 70 mol%.
50 mol%, and the above ethylene and propylene further contain dichloropentadiene (DCPD), ethylidenenorbornene (ENB),
An ethylene-propylene-diene terpolymer copolymerized with 1,4-hexadiene (1,4HD), etc., the amount of the third component represented by the iodine value is 8 to 8.
25, preferably 9 to 15, raw rubber Mooney viscosity is 30
~70 can be mentioned. Examples of the above-mentioned resins include EP21, EP51 [all manufactured by Nippon Gosei Rubber Co., Ltd.], Esplen 301, Esplen 501 [all manufactured by Sumitomo Chemical Co., Ltd.], EPT4021, EPT1045 [all manufactured by Mitsui Petrochemical Co., Ltd.], etc. Ru. Still other preferred olefinic resins include copolymers of ethylene and vinyl acetate having a vinyl acetate content of 2 to 50% by weight and an MI of 1 to 30. Examples include Levaprene 450,
Examples include Levaprene 452 (all manufactured by Bayer), Evatate-D2021, H2031, K2010 (all manufactured by Sumitomo Chemical), and NUC8450, 3145 (all manufactured by Nippon Unicar). In the present invention, the above olefin resin is
The seeds may be used alone, or two or more types may be mixed (blended) and used. The olefin resin may be crosslinked. As this cross-linked olefin resin, a wide variety of conventionally known ones can be used. Specifically, the above-mentioned olefin-based resin is cross-linked by adding an organic peroxide and heat-treated, and the above-mentioned olefin-based resin is heated and cross-linked. Examples include crosslinked olefin resins obtained by irradiation with water, and crosslinked water-crosslinkable olefin resins. It is necessary to incorporate hydrated alumina and/or hydrated magnesia as a flame retardant into the composition of the present invention. As the hydrated alumina used in the present invention, a wide variety of conventionally known hydrated aluminas can be used, such as
Al ₂ O ₃・nH ₂ O (n indicates 2.5 to 3.5), etc., more specifically Hygilite H42M [manufactured by Showa Light Metal Co., Ltd.],
Examples include B1403, B1403-D-18 [both manufactured by Nippon Light Metal Co., Ltd.], and as the hydrated magnesia, a wide variety of conventionally known hydrated magnesias can be used, such as
Examples include MgO.mH ₂ O (m indicates 1.5 to 2.5). Among the above-mentioned hydrated magnesias, those having a specific surface area of 3 to 15 m ² /g by the BET method and 0% of particles of 5 μ or more in the particle size distribution determined by the Luzex method are particularly suitable. Specific examples include Kisuma 5B, Kisuma 5A, and Kisuma 5E (all manufactured by Kyowa Chemical Industry Co., Ltd.). In the present invention, the amount of such hydrated alumina and/or hydrated magnesia is usually 50 to 300 parts, preferably 70 parts by weight, based on 100 parts by weight of polyolefin (hereinafter simply referred to as "parts").
It is preferable to mix up to 200 parts, more preferably 90 to 150 parts. If the amount of hydrated alumina and/or hydrated magnesia exceeds 300 parts, there will be a disadvantage that the physical properties of the resulting composition will deteriorate. Further, if the amount of hydrated alumina and/or hydrated magnesia is less than 50 parts, flame retardant performance will not be exhibited. In the present invention, red phosphorus is used as a flame retardant aid.
80% or more, a loss on drying of 0.8% or less, a 74 mesh sieve residue of 7% or less, and the surface of which is coated with a thermosetting resin is blended into the composition of the present invention. is required. Examples of the thermosetting resin include phenol resin and phenol-formalin resin.
Specific examples of such red phosphorus include Novolt #120 and Novolt #120uF (both manufactured by Rin Kagaku Kogyo Co., Ltd.). In the present invention, the amount of such red phosphorus is usually 3 to 40 parts, preferably 5 to 15 parts, per 100 parts of olefin resin.
part, more preferably 5 to 12 parts.
If the amount exceeds 40 parts, there will be a disadvantage that the physical properties of the resulting composition will deteriorate. On the other hand, if the amount of the flame retardant aid is less than 3 parts, the flame retardant effect of the resulting composition will be difficult to exhibit. In the composition of the present invention, the DBP oil absorption is 100~
160cm ³ /100g and ASTM code is N330 ~
It is necessary to incorporate a specific carbon black, furnace black, recognized as N351. Carbon black other than the above-mentioned specific carbon black, such as DBP oil absorption of 30 to 50 cm ³ /
Even if 100 g of thermal carbon is used, the intended purpose of the present invention cannot be achieved at all. Examples of the above-mentioned specific carbon black include HAF or
Examples include what is called HAF-HS carbon. Specific examples include Diamond Black H, Diamond Black HS [all manufactured by Mitsubishi Chemical Corporation],
Examples include Vulcan-3, Vulcan-3H (all manufactured by Cabot Corporation), Seast H, Seast 3H (all manufactured by Tokai Electrode Co., Ltd.), and Ketstsuen Black HAF (manufactured by Ketstsuen Co., Ltd.). Among these, Diamond Black H and Vulcan-3 are preferred. In the present invention, such specific carbon black is usually added in an amount of 3 to 50 parts per 100 parts of olefin resin.
The amount is preferably 5 to 20 parts, more preferably 5 to 15 parts. If the amount exceeds 50 parts,
There is a tendency for the resulting composition to harden and lose its mechanical properties. On the other hand, if the amount of the flame retardant aid is less than 3 parts, it is not preferable because the ashing property will be difficult to develop. In the present invention, it is essential to use the specific red phosphorus and carbon black together. If any of these is lacking, it will be impossible to obtain a resin composition with excellent ashing properties (see Comparative Examples below). In the composition of the present invention, a coupling agent may be added as necessary. As the coupling agent, a wide variety of conventionally known coupling agents can be used, and examples include monoalkoxy type, neoalkoxy type, coordination type, chelate type titanate coupling agents and silane coupling agents. Among the titanate coupling agents mentioned above, those containing phosphorus are preferred. The coordination type titanate coupling agent containing phosphorus has 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. ] Preferred examples include organic titanates represented by the following. A specific example is tetraisopropyl di(dioctylphosphite) titanate [KR-
41B, manufactured by Kenrichi Co., Ltd.], tetraoctyl di(ditridecyl phosphite) titanate [KR-
46B, manufactured by the same company], tetraisopropyl di(dilauryl phosphite) titanate [KR-36C,
Examples include tetra(2,2-diallyloxymethyl-1-butoxy)di(ditridecyl)phosphite titanate [KR-55, manufactured by the same company]. As a chelate type titanate coupling agent, the general formula [In the formula, R represents an acyl group, a sulfonyl group, a phosphoryl group, or an aryl group. X is >CK ₂ or >
Indicates C=O. ] Preferred are organic titanates represented by the following, specifically diisostearoyloxyacetate titanate [KR-101, manufactured by Kenrichi Co., Ltd.], isostearoyl methacryloxyacetate titanate [KR-106, manufactured by the same company], isostearoyl acryloxy Acetate titanate [KR-110S, manufactured by the same company], di(dioctyl phosphate) oxyacetate titanate [KR-112S, manufactured by the same company], 4-aminobenzenesulfonyldodecylbenzenesulfonyloxyacetate titanate [KR-126S, manufactured by the same company] ], dimethacryloxyacetate titanate [KR-
133CS, manufactured by the same company], dicumyl phenolate oxyacetate titanate [KR-134S, manufactured by the same company], 4-aminobenzoyl isostearoyloxyacetate titanate [KR-137BS, manufactured by the same company], di(dioctylpyrophosphate) Oxyacetate titanate [KR-138S, manufactured by the same company], diacryloxyacetate titanate [KR-139CS, manufactured by the same company], di(dioctyl, butyl pyrophosphate) oxyacetate titanate [KR-158FS, manufactured by the same company], Diisostearoyl ethylene titanate [KR-201, manufactured by the same company], di(dioctyl phosphate) ethylene titanate [KR-212, manufactured by the same company], 4-aminobenzenesulfonyldodecylbenzenesulfonyl ethylene titanate [KR-226S, manufactured by the same company] Dimethacrylic ethylene titanate [KR-233, manufactured by the same company], Di(dioctyl pyrophosphate (ethylene titanate) [KR-238S, manufactured by the same company],
Dianthranyl ethylene titanate [KR-252,
Examples include di(butyl, methyl pyrophosphate) ethylene titanate [KR-262ES, manufactured by the same company] and the like. As the silane coupling agent, 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-methacrylate Roxypropyltrimethoxysilane [A174, manufactured by Nippon Unicar], β
-(3,4-epoxycyclohexyl)ethyltrimethoxysilane [A186, manufactured by Nippon Unicar],
Examples include γ-glycidyloxypropyltrimethoxysilane [SH6040, manufactured by Toray Silicone Co., Ltd.]. In the present invention, such a coupling agent is usually blended in an amount of 0.1 to 5 parts, preferably 0.2 to 3 parts, and more preferably 0.3 to 1.5 parts per 100 parts of the olefinic resin. By incorporating a coupling agent into the composition of the present invention, the mechanical strength of the resulting composition is improved, and the processability is improved. In addition to the various components mentioned above, the composition of the present invention includes:
Various known additives can be blended. Examples of such additives include naphthenic, aromatic, process oils, phthalic acid, esters, trimellitic acid, plasticizers such as epoxy resins, hindered phenols, aromatic amines, thiopropionates, etc. stabilizers, fillers such as mistron vapor talc, calcium carbonate, magnesium carbonate, phthalocyanine blue, chrome yellow,
Pigments such as red iron, stearic acid, oleic acid,
Examples include lubricants such as higher fatty acid metal salts, processing aids, and the like. The amount of these various additives can be appropriately determined within a wide range, but usually 5 to 50 parts of plasticizer is added to 100 parts of the total weight of the four essential components.
0.1 to 5 parts of stabilizer, 10 to 200 parts of filler, and pigment.
0.1-10 parts, lubricant 0.1-5 parts, processing aid 0.1-10
It is best to mix it in parts. The composition of the present invention can be obtained by suitably blending predetermined amounts of the above-mentioned various components and uniformly mixing them according to conventionally known methods using a Banbury mixer, a Henschel mixer, or the like. Although all of the above components can be mixed at the same time, it is preferable to add the coupling agent at the same time as the filler is added. In addition, in a polymer blend system, it is preferable to mix the polymer uniformly first and then mix the other components. When 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 mixed according to the purpose. It may be formed into various shapes. Effects of the Invention Because the composition of the present invention is halogen-free, it does not emit smoke even when left in a high-temperature flame such as during a fire, and it does not emit corrosive or acidic gases due to thermal decomposition. Moreover, it has excellent flame retardancy, mechanical strength, ashing properties, electrical properties, aging resistance, etc. Therefore, the composition of the present invention is suitable as a coating material for building materials, pipes, hoses, sheets, seat covers, wall materials, electric cables (internal insulators, external sheaths, etc.), and the like. Examples Examples will be given below to explain the present invention in more detail. The characteristics of the samples obtained in each example were tested by the following method. <Flame retardancy test> After uniformly kneading the composition of the present invention using a roll mill, a sheet sample with a thickness of 3.0 mm was prepared by hot press molding. Calculate the index (LOI) and evaluate flame retardancy. <Mechanical properties> Sample sheet similar to the above (sheet samples with a thickness of 1 mm for compositions No. 1 to 13 of Example 1 described later, sheet samples with a thickness of 2 mm for compositions No. 14 to 18)
Each characteristic will be investigated using the following method. (1) 100% modulus (Kg/mm ² ) according to ASTM D882. (2) 200% modulus (Kg/mm ² ) according to ASTM D882. (3) Tensile strength (Kg/mm ² ) According to ASTM D882. (4) Elongation (%) According to ASTM D882. (5) Hardness (Shore A, O seconds value) According to ASTM D882. <Specific gravity> Measure in accordance with JIS K 6350 on the same sample sheet used in the above flame retardancy test. <Electrical properties (room temperature)> After uniformly kneading the composition of the present invention using a roll mill, a sheet sample with a thickness of 1 mm was prepared by hot press molding. Find (ohm−cm). <Aging characteristics> The same sample sheet used in the above electrical test was aged at 100°C x 10 days and then at 135°C according to ASTM D573.
Tensile strength retention (%) and elongation retention (%) are determined after ×7 days and after 150°C ×7 days. <Ashing characteristics> A sample with the same shape as the flame retardant test is placed on a wire mesh and burned from below with a burner. After burning for 1 minute, remove the burner, and immediately after the afterflame, place the sample together with a wire mesh on a horizontal perlite plate, and drop a 5 g iron ball from 1 cm above the sample to see if the ash layer collapses. was observed, and the ashing characteristics were evaluated according to the following criteria. 5: There is no damage to the ash layer even if a ball falls. 4: The ash layer does not break, but cracks appear. 3: The ash layer cracks into 2 to 5 small pieces. 2: The ash layer is broken into many small pieces. 1: The ash layer is crushed into pieces. Example 1 A composition of the present invention was obtained by mixing predetermined amounts (parts by weight) of each component shown in Table 1 below using the following method. That is, a base polymer, a flame retardant, a flame retardant aid, and carbon black were uniformly mixed in a roll mill, and then a sheet-like composition was prepared. The conditions at this time are
120 to 140°C for compositions No. 1 to 6;
For compositions No. 7 to 11, the temperature was 100 to 130°C, and for compositions No. 12 to 16, the temperature was from room temperature to 80°C. In addition, each of the above compositions was heated at 100% by heat press.
Sheets of each composition were prepared by molding or mold crosslinking under a pressure of ~150 Kg/cm ² . The conditions at this time were 150°C for 5 minutes for compositions No. 1 to 6.
For Nos. 7 to 13, 170°C for 45 minutes, composition No. 14
-18, the temperature was 165°C for 30 minutes.

[Table] In Table 1, the symbols for each component indicate the following. <Base polymer> A-1...Low-density polyethylene (manufactured by Mitsui Petrochemicals, "Urtozex" 202OL, MI=2.1,
Density = 0.920) A-2...Low density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd.,
"Yukalon" LLF30F, MI=1.0, density=
0.920) A-3...Ethylene vinyl acetate copolymer (manufactured by Nippon Unicar Co., Ltd., NUC8450, VA content = 15wt%,
MI=2.0) A-4... Ethylene vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Evatate K2010, VA content = 25wt
%, MI=3.0) A-5...Poly-α-olefin (manufactured by Mitsui Petrochemical Co., Ltd., Tafmar A4090, MI=4.0, density 0.89) A-6...Poly-α-olefin (manufactured by Mitsui Petrochemical Co., Ltd., Tafmar P0480, MI = 1.2, density 0.88 A-7...EPDM (manufactured by Japan Synthetic Rubber Co., Ltd., EP21, Mooney viscosity = 38, third component = ENB, iodine value = 19) A-8...EPDM (manufactured by Sumitomo Chemical Co., Ltd., Espren
501A, Mooney viscosity = 43, third component =
NEB, iodine value = 12) <Flame retardant> B-1-Mg(OH) ₂ (manufactured by Kyowa Kagaku Co., Ltd., Kisuma 5B) <Flame retardant aid> C-1...Red phosphorus (manufactured by Rin Kagaku Co., Ltd., Novaretsud #120 ) <Carbon black> D-1...HAF carbon (manufactured by Mitsubishi Kasei Corporation, Diamond Black H) D-2...HAF carbon (Vulcan-3, manufactured by Kayabot Corporation) <Additives> E-1...Coordination type titanium coupling Agent (manufactured by Kenrichi Co., Ltd., KR41B, [tetraisopropyl di(dioctyl phosphite) titanate]) E-2... Coordination type titanium coupling agent (manufactured by Kenrichi Co., Ltd., KR46B, [tetraoctyl di(ditridecyl phosphite) titanate]) ) E-3... Chelate type titanium coupling agent (manufactured by Kenrichi Co., Ltd., KR101, [diisostearoyloxyacetate titanate)] E-4... Chelate type titanium coupling agent (manufactured by Kenrichi Co., Ltd., KR201, [diisostearoyl ethylene titanate) ]) E-5... Silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A172, [vinyl-tris (β-methoxyethoxysilane)]) E-6... Silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A174, [γ-methoxysilane]) Roxypropyltrimethoxysilane]) E-7... Mistron vapor talc (magnesium silicate) E-8... Stearic acid E-9... Zinc stearate E-10... Zinc oxide E-11... Triallylisocyanurate E-12 ...N,N'-m-phenylene bismaleimide E-13...Dicumyl peroxide E-14...Process oil (naphthenic, manufactured by Nippon Sun Oil Co., Ltd., Sansen 4240, viscosity = 15 to 20 cst,
Specific gravity 0.920) E-15...Mercaptobenzimidazole E-16...Anti-aging agent (manufactured by Ouchi Shinko Co., Ltd., Nokuratsuku)
300, 4,4'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethyl-diphenyl sulfide) E-17...Irganox 1010 (manufactured by Ciba Geigy,
Tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl,)
Propionate]Methane) The properties of the molded sheet samples of the compositions of the present invention obtained in each of the above examples are shown in Table 2 below.

[Table] Residual tensile strength − − −
− − − − −
Remaining elongation rate − − −
− − − − −
150℃, 7 days

Tensile strength residual rate − − −
− − − 102 106
Remaining elongation rate − − −
− − − 99 98

Claims (1)

[Claims] 1 100 parts by weight of olefin resin, 50 to 300 parts by weight of hydrated alumina and/or hydrated magnesia, red phosphorus content of 80% or more and dry weight of 0.8% or less,
74 Mesh sieve residue is 7% or less, the surface is coated with thermosetting resin, 3 to 40 parts by weight of red phosphorus, and DBP oil absorption is 100 to 160 cm ³ /100 g.
1. A flame-retardant resin composition, characterized in that it contains 3 to 50 parts by weight of a furnace black whose ASTM code is N330 to N351.