JPH0129502B2 - - 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 recent years, a composition made by mixing 20-30% by weight of a thermoplastic resin mainly composed of polypropylene with 80-70% by weight of an inorganic filler consisting of aluminum hydroxide and magnesium hydroxide, : A resin composition with excellent insulation resistance has been developed in which the blending ratio of magnesium hydroxide is 60:40 to 30:70 by weight (Japanese Patent Laid-Open No. 121058/1983). According to this publication, it is said that when the amount of thermoplastic resin blended exceeds 30% by weight, the flame retardance of the resulting resin composition decreases. However, although this resin composition has excellent flame retardancy and insulation resistance, it has the disadvantage of being insufficient in terms of mechanical strength (especially elongation properties) and aging resistance (comparative examples described later). (See Nos. 6 to 8). Furthermore, a resin composition with excellent electrical properties, flame retardance, etc., which is made by adding an inorganic flame retardant and polyethylene wax to an ethylene-butene copolymer, has also been developed (see JP-A-57-87010). ). However, the resin compositions described in this publication also have the disadvantage of being insufficient in terms of mechanical strength (especially elongation properties) and aging resistance (Comparative Examples Nos. 9 and 10 described later).
reference). Means for Solving the Problems The object of the present invention is to provide a flame retardant material that is halogen-free, has excellent flame retardancy and electrical properties, and also has excellent mechanical strength (especially elongation properties) and aging resistance. An object of the present invention is to provide a resin composition. 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, the present invention provides an essentially linear low-density polyethylene obtained by polymerizing ethylene under low pressure using (A) (1) an olefin having 4 to 10 carbon atoms as a comonomer and a catalyst; (2) a copolymer of ethylene polymerized with a Ziegler catalyst and an α-olefin having 4 to 8 carbon atoms, with a melt index of 0.91 to 0.96 and a melt index of 0.1 to 10; 1 to 10, density 0.85 to
Poly-α-olefin and (3) MFR in the range of 0.90
at least two selected from the group consisting of polypropylene having a density of 0.1 to 5 and a density of 0.88 to 0.91.
and (B) 70 to 200 parts by weight of hydrated alumina and/or hydrated magnesia. Component (A) used as the base polymer in the present invention is a blend polymer of at least two types selected from the above (1) to (3). The polymer (1) above is an 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, and has a density of 0.91 to 0.96. It is a low density polyethylene with a melt index (MI) ranging from 0.1 to 10. Specific examples include Yucalon-LL, F-30F, F-30H [all made by Mitsubishi Yuka Co., Ltd.], Urtozex 2020L, 3520F, 3021F [all made by Mitsui Petrochemical Co., Ltd.], DF-DA-7540 [Union [Made of carbide] etc. The polymer (2) above is a copolymer of ethylene and α-olefin having 4 to 8 carbon atoms polymerized using a Ziegler catalyst, and has an MI of 1 to 10 and a density of 0.85.
It is a poly α-olefin in the range of ~0.90. Specific examples include Tafmar A-4090, A-
Examples include 4085, P-0180, and P-0480 (all manufactured by Mitsui Petrochemicals). The polymer in (3) above has an MFR of 0.1 to 5 and a density of
0.88-0.91 polypropylene. Specific examples include BC8-D, EC9 [all manufactured by Mitsubishi Yuka Co., Ltd.], SB210, F301 [all manufactured by Mitsui Petrochemical Co., Ltd.], E250G [manufactured by Idemitsu Oil Co., Ltd.], MK112 [manufactured by Showa Denko Co., Ltd.], etc. can be exemplified. The polypropylene preferably has an MFR of 0.1 to 5.0 and a density of 0.89 to 0.91. When using a blend of the above polymers (1) and (2), the mixing ratio of the two is usually 30-70:70-30, preferably 40-60: It is best to set it between 60 and 40. When using a blend of the above polymers (2) and (3), the mixing ratio of the two is usually the former:the latter at a weight ratio of 30-70:70-30, preferably 40-60:
It is best to set it between 60 and 40. Furthermore, when the above polymers (1) and (3) are used as a blend, the mixing ratio of the two is usually 30-70:70-30 by weight, preferably 30-70:70-30. is 40
~60: It is best to set it to 60-40. Furthermore, when using a blend of the above polymer (1), polymer (2), and polymer (3), the weight ratio of the polymer (1) and the polymer (2) is 30 to 30. It is preferable to mix 66 to 150 parts of the polymer (3) to 100 parts by weight (hereinafter simply referred to as "parts") of the mixture blended at a ratio of 70:70 to 30. 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 H-42M [manufactured by Showa Light Metal Company], B1403, B1403S [all manufactured by Nippon Light Metal Company]
As the hydrated magnesia, a wide variety of conventionally known hydrated magnesias can be used, such as MgO.
Examples include mH ₂ O (m indicates 1.5 to 2.5). Among the above hydrated magnesias, those with a specific surface area of 3 to 15 m ² /g by the BET method and 5μ or more in the particle size distribution by the Luzex method are 0%.
It is preferable that As a specific example,
Examples include Kisuma 5B, Kisuma 5A, and Kisuma 5E (all manufactured by Kyowa Chemical Industry Co., Ltd.). In the present invention, such hydrated alumina and/or hydrated magnesia is usually blended in an amount of 70 to 200 parts, preferably 90 to 150 parts, per 100 parts of component (A). If the amount of hydrated alumina and/or hydrated magnesia exceeds 200 parts, there will be a disadvantage that the physical properties of the resulting composition will deteriorate. Furthermore, if the amount of hydrated alumina and/or hydrated magnesia is less than 50 parts, there will be a drawback that the flame retardancy of the resulting composition will be reduced. In the present invention, when the polymer (3) is used as the component (A), it is particularly preferable to incorporate a copper damage inhibitor into the composition of the present invention. As the copper damage inhibitor used, a wide range of conventionally known ones can be used.
For example, N,N'-bis(3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl)
Examples include hydrazine, (3-(N-salicyloyl)amino-1,2,4-tetrazole), N,N'-dibenzaloxalyl dihydrazide, and N,N'-disalicylidene oxalyl hydrazide.
The amount of the copper damage inhibitor is usually 0.02 to 5 parts, preferably 0.1 to 2 parts, per 100 parts of the polymer (3) above.
It is better to make it a department. Even if the amount of the copper damage inhibitor exceeds 5 parts, the effect of adding the copper damage inhibitor does not improve much, and this is not economically preferable. Furthermore, if the amount of the copper damage inhibitor is less than 0.02 parts, the effect of preventing copper damage will be difficult to exhibit. In the present invention, red phosphorus, zinc borate, titanium dioxide, etc. can be blended into the composition of the present invention as flame retardant aids. Here, as the red phosphorus, a wide variety of commercially available products can be used. For example, red phosphorus with a red phosphorus content of 80% or more, a loss on drying of 0.8% or less, and a 74 mesh sieve residue of 7% or less. preferable. In addition, the surface of the red phosphorus is phenol-
Those coated with a thermosetting resin such as formalin resin are also preferred. Specific examples thereof include Novolt #120 and Novolt #120uF (both manufactured by Rin Kagaku Kogyo Co., Ltd.). In addition, as zinc borate, conventionally commercially available products can be widely used, such as chemical formula 2ZnO.
It is preferably represented by 3B ₂ O ₃ .3.5H ₂ O, has a particle size of 2 to 10 μm, and a crystal density of 2.6 to 2.8 g/cm ³ . A specific example is zinc borate 2335 [UK
[manufactured by Bora×], etc. As titanium dioxide, conventionally commercially available titanium dioxide can be widely used, for example, at least 90% or more.
Contains TiO ₂ and has a particle size that passes through a 100 mesh sieve, containing at least 90% TiO ₂ ,
Preferred examples include those with a 149μ sieve residue of 0% and a moisture content of 0.7% or less. More specifically, examples include Titone A-150 and Titone R-650 (both manufactured by Sakai Chemical Industry Co., Ltd.). In the present invention, such a flame retardant aid is usually used in a proportion of 100% of component (A).
3 to 50 parts, preferably 5 to 20 parts, more preferably 5 to 15 parts. If the amount exceeds 50 parts, the physical properties of the resulting composition tend to deteriorate, which is not preferable. On the other hand, if the amount of the flame retardant aid is less than 3 parts, the resulting composition tends to have lower flame retardancy, which is not preferable. A coupling agent may be added to the composition of the present invention. As a coupling agent,
A wide variety of conventionally known coupling agents can be used, including 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' is carbon number 3~
30 alkyl groups are shown. Preferred examples include organic titanates represented by the following. Examples include tetraisopropyl di(dioctyl phosphite) 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, manufactured by the same company] Tetra(2,2-diallyloxymethyl-1-butoxy) di(di-tridecyl) 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 represents CH ₂ or 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] [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, among the above coupling agents,
It is particularly preferred to incorporate chelating and/or coordinating titanate coupling agents into the compositions of the invention. In the present invention, such a coupling agent is usually used in an amount of 0.05 to 5 parts, preferably 0.2 to 3 parts, per 100 parts of component (A).
part, more preferably 0.3 to 1.5 parts. If the amount of coupling agent exceeds 5 parts,
A disadvantage arises in that the mechanical properties of the resulting composition tend to be impaired. Furthermore, if the amount of the coupling agent added is less than 0.1 part, the effect of the addition of the coupling agent will be difficult to exhibit. 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 ranges, hindered phenols, aromatic amines, thiopropionates, etc. stabilizers, mistron vapor talc, clay, fillers such as calcium carbonate, magnesium carbonate, pigments such as phthalocyanine blue, chrome yellow, red iron, lubricants such as stearic acid, oleic acid, higher fatty acid metal salts, processing aids, etc. can be exemplified. The amounts of these various additives can be appropriately determined within a wide range, but usually 5 to 50 parts of plasticizer, 0.1 to 5 parts of stabilizer, per 100 parts of the total weight of the two essential components, 10-200 fillers
0.1 to 10 parts of pigment, 0.1 to 5 parts of lubricant, and 0.1 to 10 parts of processing aid. 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 molded 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, 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 3.5 mm was prepared by hot press molding. Calculate the index (LOI) and evaluate flame retardancy. <Mechanical properties> For the same sample sheet (1 mm thick) as above,
Examine each characteristic 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. <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> For the same sample sheet used in the above electrical test, the tensile strength retention (%) and elongation retention (%) after 10 days at 100°C are determined according to ASTM D573. 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 and a flame retardant were uniformly mixed in a roll mill, and then a sheet-like composition was prepared. The conditions at this time were in the range of 160 to 180°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 at 180° C. for 10 minutes under a pressure of ~150 Kg/cm ² .

【table】

[Table] In Table 1, the symbols for each component indicate the following. <Base polymer> A-1...Low density polyethylene (manufactured by Mitsui Petrochemical Co., Ltd., "Urtozex" 202DL, 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...Low-density polyethylene (Mitsui Petrochemical Co., Ltd., "Urtozex" UZ3550R, MI
= 4.5, density = 0.920) A-4...Low density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd.,
"Yukalon" LL9150M, MI = 5.0, density = 0.919) A-5...Poly-α-olefin (manufactured by Mitsui Petrochemicals, Tafmar A4090, MI = 4.0, density =
0.89 A-6...Poly-α-olefin (manufactured by Mitsui Petrochemicals, Tafmar A0480, MI=1.2, density
0.88 A-7... Polypropylene (BC-8D, manufactured by Mitsubishi Yuka Co., Ltd.) A-8... Polypropylene (BC-8D, manufactured by Mitsubishi Yuka Co., Ltd.) A-9... Polypropylene (SB210, manufactured by Mitsui Petrochemical Co., Ltd.) A- 10…Polypropylene (E-250, manufactured by Idemitsu Petrochemical Co., Ltd.) <Fuel-resistant> B-1…Mg(OH) ₂ (manufactured by Kyowa Chemical Co., Ltd., Kisuma 5B) B-2…Al(OH) ₃ (Nippon Light Metal Industry Co., Ltd.) Made by
B1403S) <Additives> C-1... Red phosphorus (manufactured by Rin Kagaku Co., Ltd., Novaretsudo #120) C-2... Coordination type titanium coupling agent (manufactured by Kenrichi Co., Ltd., KR41B, [Tetraisopropyl di(dioctyl phosphite) titanate) ]) C-3... Coordination type titanium coupling agent (manufactured by Kenrichi Co., Ltd., KR46B, [tetraoctyl di(ditridecyl phosphite) titanate]) C-4... Chelate type titanium coupling agent (manufactured by Kenrichi Co., Ltd., KR101, [Diisostearoyloxyacetate titanate]) C-5...Chelate type titanium coupling agent (manufactured by Kenrich Co., Ltd., KR201, [diisostearoyl ethylene titanate]) C-6...Silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A172, [Vinyl-tris (β-methoxyethoxysilane)] C-7... Silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A174, (γ-methacryloxypropyltrimethoxysilane)) C-8... Stearic acid C-9... Stearin Zinc acid C-10…Seanox 412S (manufactured by Shiraishi Calcium Co., Ltd.) C-11…Irganox 1010 (manufactured by Ciba Geigy Co., Ltd.)
Tetrakis [methylene-3-(3,5-
di-t-butyl-4-hydroxyphenyl)propionate]methane) C-12...Copper damage inhibitor (N,N'-bis[3-(3',
5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hydrazine C-13...Copper damage inhibitor (N,N'-dibenzyloxalyl hydrazide) C-14...Copper damage inhibitor (N,N '-Disalicylidene oxalyl hydrazide) The properties of the molded sheet samples of the compositions of the present invention obtained in the above examples are shown in Table 2 below.

[Table] From Table 2 above, it can be seen that the sheet obtained using the composition of the present invention has excellent properties. Example 2 and Comparative Example 1 A mixture of a predetermined amount (parts by weight) of each component shown in Table 3 below was treated in the same manner as in Example 1 above to produce a flame-retardant resin composition and a sheet of these compositions. Obtained. In Table 3, the symbols for each component indicate the following. <Base polymer> A-11... Polyethylene (density = 0.925) A-12... Ethylene-butene copolymer A-13... Ethylene-propylene block copolymer <Additive> C-15... Polyethylene wax Table 3 above The flame retardancy, mechanical properties (100% modulus, tensile strength and elongation) and aging properties (tensile strength retention and elongation retention) of each composition or sheet shown in were investigated in the same manner as above, and the results are summarized in Table 3. Shown.

[Table] The following can be seen from Table 3 above. Comparison No. 6-10
All of the compositions of the present invention (No. 1 to 1) are the compositions of the present invention (No.
It is inferior to 5) in terms of mechanical properties (especially elongation properties) and aging properties.

Claims (1)

[Scope of Claims] 1 (A) (1) An 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, comprising: Low density polyethylene with density ranging from 0.91 to 0.96, melt index 0.1 to 10,
(2) A copolymer of ethylene and α-olefin having 4 to 8 carbon atoms polymerized using a Ziegler catalyst, with a melt index of 1 to 10 and a density of 0.85.
poly-α-olefin in the range of ~0.90 and (3)
100 parts by weight of at least two selected from the group consisting of polypropylene having an MFR of 0.1 to 5 and a density of 0.88 to 0.91; and (B) 70 to 70 parts of hydrated alumina and/or hydrated magnesia.
A flame-retardant resin composition containing 200 parts by weight.