JPS61213237A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide a halogen-free composition free from generation of smoke and toxic gas even in a flame, by compounding hydrated alumina or hydrated magnesia to >=2 polymers selected from a specific polypropylene, a low-density polyethylene and a poly-alpha-olefin. CONSTITUTION:The objective composition can be produced by compounding (A) 100pts.wt. of at least two kinds of polymers selected from (A1) a straight- chain low-density polyethylene having a density of 0.91-0.96 and an MI of 0.1-10 and obtained by the polymerization of ethylene under low pressure in the presence of a catalyst using a 4-10C olefin as a comonomer, (A2) a poly-alpha-olefin having an MI of 1-10 and a density of 0.85-0.90 and obtained by the copolymerization of ethylene and a 4-8C alpha-olefin in the presence of a Ziegler catalyst and (A3) a polypropylene having an MFR of 0.1-5 and a density of 0.88-0.91 with (B) 50-300pts.wt., preferably 90-150pts.wt. of hydrated alumina and/or hydrated magnesia.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a flame retardant resin composition.

BACKGROUND ART Conventionally, flame-retardant resin compositions made of halogen-containing polymers or non-halogen-based polymers and organic halogen-based flame retardants 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.

An object of the present invention is to provide a flame-retardant composition that is halogen-free, has excellent flame retardancy, mechanical strength, electrical properties, aging resistance, etc., and has good processability. shall be.

Structure of the Invention That is, the present invention provides (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; (2) low-density polyethylene having a density of 0.91 to 0.96 and a melt index of 0.1 to 10;
A poly-α-olefin that is a copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms polymerized with a Ziegler catalyst, and has a melt index of 1 to 10 and a density of 0.85 to 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) hydrated alumina and/or hydrated magnesia 50
The present invention relates to a flame-retardant resin composition characterized by containing ~3001i parts.

The component (^) 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 10. 0°96, and a melt index (Ml) of 0.1 to 10. Specific examples include Yucalon-LL, F-30F.
Examples include %F-30H (all manufactured by Mitsubishi Petrochemical Co., Ltd.), Urtozex 202OL, 3520F, and 3021 F (all manufactured by Mitsui Petrochemical Co., Ltd.), and DF-OA-7540 (manufactured by Union Carbide).

The polymer (2) above is a copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms polymerized with a Ziegler catalyst, and has an Ml of 1 to 10 and a density of 0.85 to 0.90.
It is a poly-α1-olefin in the range of . Specific examples include Tafmer A-4090, A-4085, P-0
180, P-0480 (all manufactured by Mitsubishi Yuka Co., Ltd.), and the like.

The polymer (3) above is polypropylene having a VFR of 0.1 to 5 and a density of 0.88 to 0.91. Specific examples include BO2-D, EC9 (all manufactured by Mitsubishi Yuka), 5B210%F301 (all manufactured by Mitsui Petrochemical), E250G (manufactured by Idemitsu Oil), MK112 (manufactured by Showa Denko), etc. can be exemplified. The above polypropylene has a VFR of 0.1 to 5.0 and a density of 0.89 to 0.9.
1 is preferred.

When the above polymers (1) and (2) are used as a blend, the mixing ratio of the two is usually 30-70:70-30, preferably 40-60: It is preferable to set it to 60-40. Even when the above polymers (2) and (3) are used as a blend, the mixing ratio of the two is usually:
The weight ratio of the latter is 30-70, preferably 40
-60: It is preferable to set it to 60-40. Also, the above (
When using a blend of the polymer 1) and the polymer (3), the mixing ratio of the two is usually 30 to 70, preferably 40 to 70, by weight. 60: It is preferable to set it to 60-40. Furthermore, the polymer of (1) above, the polymer of (2) and (3)
When using a blend of polymers (1) and (2), the weight ratio of the former to the latter -30
~70 Nia blended mixture in a ratio of 0 to 30 100
It is preferable to mix 66 to 150 parts of the polymer (3) based on parts by weight (hereinafter simply referred to as "parts").

The composition of the present invention contains hydrated alumina and/or as flame retardants.
Alternatively, it is necessary to incorporate hydrated magnesia. As the hydrated alumina used in the present invention, a wide variety of conventionally known hydrated aluminas can be used, such as AQe Os ・nH2O(n
indicates 2.5 to 3.5), more specifically Hysilite H-42M (manufactured by Showa Light Metal Co., Ltd.), 81403.81
4038 (all manufactured by Nippon Light Metal Co., Ltd.), and as the hydrated magnesia, a wide range of conventionally known hydrated magnesias can be used, such as MgO-nH2O (m is 1.5 to 2.5). can. Among the above-mentioned hydrated magnesias, those having a specific surface area of 3 to 15 m210 by the BET method and 0% of particles of 5 microns or more in the particle size distribution determined by the Luzex method are particularly suitable. Specific examples include Kisuma 75B, Kisuma 5A, Kisuma 5E (all manufactured by Kyowa Chemical Industry Co., Ltd.), etc. In the present invention, such hydrated alumina and/or hydrated magnesia are usually used in the above (A
) 50 to 300 parts, preferably 7 parts per 100 parts of the component.
It is preferable to mix 0 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. Additionally, hydrated alumina and/or
Alternatively, if the amount of hydrated magnesia is less than 50 parts, 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 variety of conventionally known ones can be used, such as N,N'-bis(3-(3',5'-di-tert-butyl-4),
'-Hydroxyphenyl)propionyl)hydrazine,
(3-(N-salicyloyl)amino-1,2,4-tetrazole), N,N'-dibenzaloxalyl dihydrazide, N,N'-disalicylideneoxalyl hydrazide, and the like. The amount of the copper damage inhibitor is usually 0.02 to 5 per 100 parts of the polymer (3) above.
part, preferably 0.1 to 2 parts. 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. Moreover, if the amount of the copper damage inhibitor is less than 0.02 parts, the effect of preventing records will be difficult to be exhibited.

In the present invention, red phosphorus, zinc borate,
Titanium dioxide and the like can be incorporated into the composition of the present invention. Here, as the red phosphorus, conventionally commercially available ones can be widely used, for example, the red phosphorus content is 80% or more,
Loss on drying is 0.8% or less and 74 mesh sieve residue is 7%
The following are preferred. It is also preferable that the surface of the red phosphorus is coated with a thermosetting resin such as phenol-formalin resin. Specific examples include No Bullet #120 and No Bullet #120! F [all manufactured by Rin Kagaku Kogyo Co., Ltd.], and the like.

Furthermore, as zinc borate, conventionally commercially available ones can be widely used, for example, those with the chemical formula 2Zn0.3BpOs.3
．． 5H20, a particle size of 2 to 10 μm, and a crystal density of 2.6 to 2.80/Cm 3 is preferable.

A specific example is zinc borate 2335 (UK 13o
(manufactured by RAX), etc.

As titanium dioxide, conventionally commercially available titanium dioxide can be widely used, for example, titanium dioxide of at least 90% or more.
and whose particle size passes through a 100 mesh sieve, and those which contain at least 90% TlO2, have a 149μ sieve residue of 0%, and have a water content of 0.7% or less.

More specifically, Taitone A-150, Taitone R
-650 (all manufactured by Sakai Chemical Industry Co., Ltd.), and the like.

In the present invention, such a flame retardant aid is usually blended in an amount of 3 to 50 parts, preferably 5 to 2 parts, and more preferably 5 to 15 parts, per 100 parts of component (A).

If the amount exceeds 50 parts, the physical properties of the resulting composition tend to deteriorate, which is not preferable.

Conversely, if the amount of the flame retardant aid is less than 3 parts,
This is not preferred because the flame retardancy of the resulting composition tends to decrease.

A coupling agent may be added to the composition of the present invention. 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 % (% formula %) (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. Specific examples include tetraisoprovir di(dioctyl phosphite) titanate (KR-41B, manufactured by Kenrich);
Tetraoctyl di(ditridecyl phosphite) titanate (KR-46B, manufactured by the same company), tetraisoprovir di(dilauryl phosphite) titanate (KR-36)
Examples include tetra(2,2-diallyloxymethyl-1-butoxy)di(di-tridecyl)phosphite titanate (KR-55, manufactured by the same company).

The chelate-type titanate coupling agent has the general formula [wherein R represents an acyl group, a sulfonyl group, a phosphoryl group, or an aryl group]. X represents ';CH2 or ';C-O. ] Preferred are organic titanates represented by the following, specifically diisostearoyloxyacetate titanate (KR-101, manufactured by Kenrich Co., Ltd.), isostearoyl methacryloxyacetate titanate (KR-10).
6, manufactured by the same company], isostearoylacryloxyacetate titanate (KR-11O8, manufactured by the same company), di(
Dioctyl phosphate) oxyacetate titanate (KR-1123, manufactured by the same company), 4-aminobenzenesulfonyldodecylbenzenesulfonyloxyacetate titanate (KR-1268, manufactured by the same company), dimethacryloxyacetate titanate (KR-133O8, manufactured by the same company) ], dicumylferrate oxyacetate titanate (KR-1348, manufactured by the same company), 4-aminobenzoyl isostearoyloxyacetate titanate (
KR-137BS, manufactured by the same company], di(dioctyl pyrophosphate) oxyacetate titanate (KR-1
388, manufactured by the same company], diacryloxyacetate titanate (KR-139C8, 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-2268, manufactured by the same company), dimethacrylic ethylene titanate (KR-233, manufactured by the same company), di(dioctylpyrophosphate) ethylene titanate (KR-23)
8S, manufactured by the same company), dianthranyl ethylene titanate (KR-252, manufactured by the same company), di(butyl).

Methyl pyrophosphate) Ethylene titanate (KR
-262ES, manufactured by the same company].

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 Co., Ltd.), β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A186, manufactured by Nippon Unicar Co., Ltd.), γ-glycidyloxypropyl t-trimethoxysilane (SH6040, (manufactured by Toray Silicone), etc.

In the present invention, among the above-mentioned coupling agents, it is particularly preferable to incorporate a chelate type and/or a coordination type titanate coupling agent into the composition of the present invention.

In the present invention, such a coupling agent is usually used as component (A) 1.
0.05 to 5 parts per 00 parts, preferably 0.2 to 3 parts
part, more preferably 0.3 to 1.5 parts. If the amount of coupling agent exceeds 5 parts, the disadvantage arises 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 above-mentioned various components, various known additives may be added to the composition of the present invention. Examples of such additives include naphthenic, aromatic, process oils, phthalic acid, esters, trimellitic acid, plasticizers such as epoxy resins, hindered phenols, aromatic amines,
Stabilizers such as thiopropionates, fillers such as Mistron paper talc, clay, calcium carbonate, magnesium carbonate, phthalocyanine blue, chrome yellow,
Examples include pigments such as red iron oxide, lubricants such as stearic acid, oleic acid, higher fatty acid metal salts, and processing aids. The blending amounts of these various additives can be appropriately determined within a wide range, but usually 5 to 50 parts of plasticizer and 0.1 to 5 parts of stabilizer per 100 parts of the total weight of the above two essential components. 10 to 200 parts of filler, 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 using a Banbury mixer, Henschel mixer, etc. according to a conventionally known method. Although all of the above components can be mixed at the same time, it is better 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 mixing machine 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, or emit corrosive gas or acid gas 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 wires and cables (internal insulators, external sheaths, etc.), and the like.

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

The characteristics of the samples obtained in the 8 cases were tested by the following method.

Flame retardancy test> The composition of the present invention was mixed uniformly using a roll mill, then hot press molded to create a sheet sample with a thickness of 3.5 mm, and this sample was tested according to JISK 7201 (oxygen index method). The oxygen index (101) is determined to evaluate flame retardancy.

<Mechanical Properties> Each property of the same sample sheet (thickness 1111 mm) as above was examined by the following method.

(1) 100% modulus (ko/ms') ASTM
According to D882.

(2) 200% modulus (shun/l12) ASTM
According to D882.

(3) Tensile strength (k(+/a+s2) 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 inch was prepared by hot press molding. (o
Find h■-CS).

<Aging characteristics> For the same sample sheet used in the above electrical test, AS
Tensile strength retention (%) and elongation retention (%) after 10 days at 100°C are determined according to TM 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 an O-lumil, and then a sheet-like composition was prepared. The conditions at this time are 160 to 18
The temperature was set at 0°C.

In addition, the above compositions were heated to 100 to 15
A sheet of each composition was prepared by molding or crosslinking by molding at 180° C. for 10 minutes under a pressure of 0 KO/cm 2 .

Table 1 Assembled item NO.

base polymer A-150505050- A-2------ A-3------ A-4------ A-5252525-- A-6---2520 A-725---- A-8-25--20 A-9--25-- A-10---25- Flame retardants B-110010012070120 B-2------ Setup No.

Additive C-15101010- C-2----1,- C-3----- C-4-----1 C-510,51-- C-6--1-- C-7 -0,1--- C-8-1-1- C-9212-- C-100,30,50,51,00,5G-110,
30,50,51,00,5C-120,50,5'-
--C-13--0,50,5-C-14----0,5 Composition No.

pace polymer A-1-20--50 A-2-20--- A-360--- A-4------ A-5-6050-- A-620--5O- A-7--5O-- A-820---- A-9---50- A-10---50 Flame retardants B-1150--150100 B-2-150150-- Setup No.

678910 Additive C-1--10-- C-2--1-- C-3--- C-4---I C-5--- C-6-1 --- C-7--1-- C-8121-- C-9--1-- C-100,50,10,20,30,3G-110,
50, 60, 60, 30, 30-12-0, 30, 30
,30,I C-13-0,30,3--1" and -1405-1:-1Uni--21" in Table 1, the symbols for each component indicate the following.

Base polymer> A-1...Low density polyethylene (manufactured by Mikata Petrochemical Co., Ltd.,
[Ultozex J 202DL, Ml-2,1, density -0,920) A-2...Low density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd., "Yukalon J LLF30F, Ml-1,0, density -0,920) A-3...Low density polyethylene (manufactured by Mikata Petrochemical Co., Ltd.,
[Urtozetsu J UZ3550R, MI-4, 5,
Density -0,920> A-4...Low density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd., [Yukalon J LL9150M, Ml-5,0, density -0,
919) A-5...Poly-α-olefin (manufactured by Mikata Petrochemical Co., Ltd., Tafmer A4090, Ml-4.0, density -0.89) A-6...Poly-α-olefin (manufactured by Mikata Petrochemical Co., Ltd. Manufactured by Kagaku Co., Ltd., Tafmer A0480.Ml-1,2, density 110.88 A-7...Polypropylene (BG-80, made by Mitsubishi Yuka Co., Ltd.) A-8...Polypropylene (BG-8D, made by Mitsubishi Yuka Co., Ltd.) A-9... Polypropylene (88210, manufactured by Mikata Petrochemical Co., Ltd.) A-10... Polypropylene (E-250, manufactured by Idemitsu Petrochemical Co., Ltd.) <Flame retardant> B-1... Mo ( OH)2 (manufactured by Kyowa Kagakusha,
Kiss 75B> B-2...AQ (OH)3 (manufactured by Nippon Light Metal Industry Co., Ltd., additive) C-1...Red phosphorus (manufactured by Rin Kagaku Co., Ltd., Tsubared #120
) C-2... Coordination type titanium coupling agent (manufactured by Kenrich Co., Ltd., KR41B, [tetraisoprobil di(dioctyl phosphite) titanate]) C-3... Coordination type titanium coupling agent (manufactured by Kenrich Co., Ltd.) , KR46B1 (tetraoctyl di(ditridecyl phosphite) titanate)) C-4... Chelate type titanium coupling agent (manufactured by Kenrich, KRlol, [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... Stearin - C-9... Zinc stearate C-10. ... Seenox 4128 (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 comethane) C-12...Copper damage inhibitor (
N,N'-bis[3-(3',5'-di[-butyl-4'-hydroxyphenyl)propionyl)hydrazine C-13...Copper damage inhibitor <N,N'-dibenzyloxalyl hydrazide ) C-14...Copper damage inhibitor (N,N'-disalicylidene oxalyl hydrazide) Characteristics of the molded sheet samples of the compositions of the present invention obtained in the above eight examples are shown in Table 2 below.

Table 2 Flame retardancy (101) 29.4 30.1 3
1,7 29.4 30.1(2) -----
1xlG") 0.5 G, 81.22, 02.0 Aging characteristics 100℃, 10 days Tensile strength retention rate 95% 95
91 93 Growth rate 88 89
91 89 88 Composition N
o.

Properties 678910 Flame retardant (Lot 31.3 32,5 2
9,8 32.5 28.9 Mechanical properties (1) 0.87 0,86 0,
91 0.95 0.98 (3)
1,75 1.66 1.62 1.75 1
,88ρ(XIO150,80,51,10,80,8
Aging characteristics 100℃, 10-day tensile strength retention 88 92 96
91 89 From Table 2 above, it can be seen that the sheets obtained using the composition of the present invention have excellent properties.

(that's all)

Claims (1)

[Scope of Claims] [1] (A) (1) 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. (2) a copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms polymerized with a Ziegler catalyst; (3) a poly-α-olefin having a melt index of 1 to 10, a density of 0.85 to 0.90, and (3) an MFR of 0.1 to 5;
100 parts by weight of at least two selected from the group consisting of polypropylene having a density of 0.88 to 0.91, and (B) 50 to 3 parts by weight of hydrated alumina and/or hydrated magnesia
1. A flame-retardant resin composition, characterized in that it contains 0.00 parts by weight.