JPH10231397A - Frame-retardant polyolefin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that is improved in shape retention on burning and its flame dripping properties by formulating a flame retarded and its auxiliary agent to a specific polypropylene composition and specifying its melt flow rate. SOLUTION: (i) 0.01-5 pts. wt. of polyethylene polymer or copolymer containing >=50wt.% of ethylene polymer units another olefin, having an intrinsic viscosity [η E] of 15-100dl/g (at 135 deg.C in tetralin) is combined with (ii) 100 pts.wt. of a polypropylene homopolymer or copolymer of >=50wt.% of propylene polymer units with an ethylene block to prepare (A) a polypropylene composition with a melt flow rate(MFR) of 0.1-50g/10min (at 230 deg.C; 21.18N), a melting point (Tm) of 150-167 deg.C, a density of 0.895-0.910g/cm<3> , a melt tension of 1-20cN at 230 deg.C. (A) This resultant polypropylene composition is mixed with 4-50 pts.wt. of a flame retarder of 50-80wt.% halogen content and (C) an auciliary agent for flame retardation to give the objective composition with MFR of 0.1-50g/10min at 230 deg.C and 21.18N.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition, and more particularly to a composition having excellent flame retardancy by blending a specific polypropylene composition with a halogenated flame retardant and a flame retardant auxiliary. More specifically, the present invention relates to a flame-retardant polyolefin composition having a high melt tension of a material, excellent shape retention during combustion, and greatly improved framing drip property.

[0002]

2. Description of the Related Art Conventionally, resins used for electric appliances are:
For the purpose of preventing ignition, burning or fire caused by electrical trouble, non-combustible resins, flame-retardant resins or self-extinguishing resins are used according to required performance. For this reason, various proposals have been made for flame retardancy for olefin resins, particularly polypropylene, made of hydrocarbons because of their excellent impact resistance, rigidity, appearance and moldability. In particular, regarding the flame retardancy standard of electric appliances, the US UL standard (UL94) requires a high degree of flame retardancy depending on products or parts, and export products to the United States require selection of materials conforming to the UL standard. . In addition, the flame retardancy of electric appliances is not limited to the United States, but a high degree of flame retardancy is required in many countries such as Japan and Western Europe. For such a request,
A material using an organic flame retardant and a flame retardant auxiliary in a thermoplastic polyolefin resin can obtain self-extinguishing properties, but generates a flaming drip (fire dripping) as a secondary ignition source during combustion. As such a measure, polypropylene 30-8
0% by weight, 0.01 to 2.0 g / 10 min polyethylene
Decabrom diphenyl ether and 100 parts by weight of a composition comprising 10 to 50% by weight of an inorganic filler selected from talc, kaolinite, sericite, silica, and diatomaceous earth, And / or dodecachlorododecahydrodimethanodibenzocyclooctene 3
It has been proposed that, in a flame-retardant resin composition containing up to 35 parts by weight, the action of the polyethylene is effective for melting and dripping during combustion (Japanese Patent Publication No. 55-30739).
No.). In such a composition, the polypropylene-based flame-retardant resin has a MFR of polyethylene (190 ° C .; 21.18).
When N) is small, uniform dispersibility is lacking. For this reason, no increase in melt tension is observed, and the effect of improving shape retention during flaming or framing drip (sagging) is small.
For this reason, in the present invention, when the compounding amount is 5% by weight or less, the melt dripping property cannot be obtained. Conversely, if the blending amount is increased, the heat distortion temperature,
It shows that the rigidity and the like are reduced and the excellent properties of polypropylene are lost, which is not preferable.

As a method for increasing the melt tension and crystallization temperature of the polypropylene composition (A) as the base resin of the present invention, an organic peroxide and a crosslinking assistant are reacted with crystalline polypropylene in a molten state. Method (Japanese Unexamined Patent Publication No.
JP-A-93711, JP-A-61-152754, etc.), a low-decomposition temperature peroxide is reacted with a semi-crystalline polypropylene in the absence of oxygen to produce a gel having no free-end long-chain branching and containing no gel. (Japanese Unexamined Patent Publication No.
298536) and the like.

In addition, as other methods for improving melt viscoelasticity such as melt tension, there have been proposed a composition containing polyethylene or polypropylene having different intrinsic viscosities or molecular weights, and a method of obtaining the composition by multi-stage polymerization. ing.

For example, ultra high molecular weight polypropylene 2
A method in which 30 parts by weight is added to 100 parts by weight of ordinary polypropylene and extruded in a temperature range from a melting point to 210 ° C. (Japanese Patent Publication No. 61-28694), wherein the intrinsic viscosity ratio obtained by a multistage polymerization method is 2 or more. Extruded sheet made of two-component polypropylene (Japanese Patent Publication 1-1)
No. 2770), a method of obtaining a polyethylene composition by melt-kneading or multi-stage polymerization of three kinds of polyethylene having different viscosity-average molecular weights containing 1 to 10% by weight of polyethylene having a high viscosity-average molecular weight (JP-B-62-610).
No. 57), using a highly active titanium-vanadium solid catalyst component, a limiting viscosity of 20 dl / g by a multi-stage polymerization method.
A polymerization method for polyethylene in which the above ultrahigh molecular weight polyethylene is polymerized in an amount of 0.05 to less than 1% by weight (JP-B 5-
No. 79683) Using a highly active titanium catalyst component pre-polymerized with 1-butene or 4-methyl-1-pentene, the intrinsic viscosity is 15 dl / g or more in a multistage polymerization method using a specially arranged polymerization vessel. 0.1% of ultra high molecular weight polyethylene
A method of polymerizing polyethylene to be polymerized by about 5% by weight (Japanese Patent Publication No. 7-8890) and the like are disclosed.

Further, polypropylene having a high melt tension is produced by polymerizing propylene using a prepolymerized catalyst in which ethylene and a polyene compound are prepolymerized to a supported titanium-containing solid catalyst component and an organoaluminum compound catalyst component. Method (Japanese Patent Publication 5-222212)
No. 2) and a method for producing an ethylene-α-olefin copolymer containing a polyethylene having an intrinsic viscosity of 20 dl / g or more by preliminarily polymerizing ethylene alone using the same catalyst component (JP-A-4-55410). Has been proposed.

In the above-mentioned various compositions and methods for producing them, although the melt tension of the polyolefin is improved to some extent, the crosslinked one lacks recyclability and has a low high-temperature rigidity. In addition, there still remain points to be improved, such as an increase in power consumption due to an increase in the motor load current of the molding machine due to the use of high-viscosity polyethylene, a limitation in productivity, and thermal stability.

In the above-mentioned multi-stage polymerization method in which the process for producing a high-molecular-weight polyolefin is incorporated into the ordinary olefin (co) polymerization process in the main polymerization, an olefin (co-polymer) for producing a trace amount of the high-molecular-weight polyolefin is used. 2.) It is difficult to control the amount of polymerization in a minute amount, and sometimes a low polymerization temperature is required to produce a polyolefin having a sufficiently high molecular weight, so that the process needs to be modified and the productivity of the final polyolefin is reduced.

In the method of prepolymerizing a polyene compound, it is necessary to prepare a polyene compound separately.
When propylene is main-polymerized after pre-polymerizing polyethylene based on a known method, the dispersibility of the pre-polymerized polyethylene in the finally obtained polypropylene composition is non-uniform, and the stability of the polypropylene composition is Further improvement is required in this respect. Also, in this document, 1-
Although the polymerization of butene is specifically described, the (co) polymerization of propylene is not specifically described.

[0010] As mentioned above, in the prior art, polypropylene is insufficient in improving the melt tension and crystallization temperature. In particular, polypropylene that is flame-retardant using a halogen-based flame retardant has not always been found to have good rigidity and moldability while ensuring shape retention and framing drip properties or melt-dropping properties during combustion. There is no present.

[0011]

SUMMARY OF THE INVENTION Under these circumstances, the present invention provides a flame-retardant resin having improved shape retention and flaming drip during combustion without impairing the mechanical properties of flame-retardant polypropylene. It is intended to provide a composition.

[0012]

In order to achieve the above object, the first flame-retardant polyolefin composition of the present invention comprises (a) an ethylene homopolymer or an ethylene polymer containing at least 50% by weight of ethylene polymerized units. -0.01 to 5 parts by weight of a polyethylene having an intrinsic viscosity [ηE] of 15 dl / g to 100 dl / g as measured in tetralin at 135 ° C, and (b) a propylene homopolymer Or a propylene-ethylene block copolymer 10 containing 50% or more of propylene polymerized units
A composition comprising 0 parts by weight, the composition having a melt flow rate (hereinafter abbreviated as MFR) [230 ° C .;
21.18N] is 0.1 to 50 g / 10min, and the melting point (Tm) is 150.
１６167 ° C., density 0.895-0.910 g / cm ³ , 2
A polypropylene composition (A) having a melt tension at 30 ° C. of 1 cN to 20 cN is used as a base resin, and 4 to 50 parts by weight of a flame retardant (B) having a halogen content of 50 to 80% by weight and a flame retardant auxiliary are used. MFR (230 ° C; 21.18
N) has a composition of a flame-retardant polyolefin composition (C) of 0.1 to 50 g / 10 min.

Next, the second flame-retardant polyolefin composition of the present invention is characterized in that the polypropylene composition (A) is used in an amount of 0.01 to 1,000 mol per 1 mol of transition metal atom containing at least a titanium compound. Organometallic compound of a metal selected from the group consisting of metals belonging to Groups 1, 2, 12 and 13 of the Periodic Table (1991 edition) [AL1]
And a polyolefin production catalyst comprising a combination of 0 to 500 mol of an electron donor [Ed1] with respect to 1 mol of a transition metal atom, and 0.01 to 100 g per 135 g of a transition metal compound component supported on the catalyst. The intrinsic viscosity [η] measured in tetralin of less than 15 dl / g is 0.01 g to 5 g per 1 g of the polypropylene (aP) and the transition metal compound catalyst component for the purpose of (co) polymerization.
Polyethylene (a-) having an intrinsic viscosity [η] of 15 to 100 dl / g measured in 000 g of tetralin at 135 ° C.
E) Propylene alone or propylene and an olefin having 2 to 12 carbon atoms are subjected to main (co) polymerization in the presence of the preactivated catalyst comprising E), and (a) containing at least 50% of an ethylene homopolymer or an ethylene polymerized unit 0.01 to 5 parts by weight of polyethylene having an intrinsic viscosity [η] of 15 to 100 dl / g measured in tetralin at 135 ° C., and (b) a propylene homopolymer or propylene A composition comprising 100 parts by weight of a propylene-olefin copolymer containing 50% by weight or more of polymerized units, wherein the composition has an MFR [230
° C; 21.18N] is 0.1 to 50 g / 10min, and the melting point (Tm) is 1.
50-167 ° C, density 0.895-0.910 g / c
m ^3, the polypropylene compositions melt tension is 1cN~20cN at 230 ° C. The (A) as a base material resin, the halogen content of 50 to 80 wt% of the flame retardant (B) 4 to 50
MFR (230 parts by weight)
C .; 21.18N) having a composition of 0.1 to 50 g / 10 min.

In the first and second flame-retardant polyolefin compositions, the flame-retardant polyolefin composition (C) or (D) has an MFR of 4 to 50 g / 10 min. Functional polyolefin composition (E).

In the first and second flame-retardant polyolefin compositions, the flame-retardant polyolefin composition (C) or (D) has an MFR of 0.1 to 4 g / 10 min.
Or a flame-retardant polyolefin composition (F) for hollow or extrusion molding.

In the first and second flame-retardant polyolefin compositions, the flame-retardant (B) blended with the flame-retardant polyolefin composition (C), (D), (E) or (F) Is decabromodiphenyl ether, 1,2-bis (2 ′, 3 ′, 4 ′, 5 ′, 6′-pentabromophenyl) ethane, N, N′ethylene-bis (tetrabromophthalimide), perchloropentacyclodecane, Dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A, tetrabromobisphenol S,
2,2-bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane and bis [[3,5-
Flame-retardant polyolefin composition (G), which is at least one halogen-based flame retardant selected from dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone
It is preferable that

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION As used herein, "polypropylene" refers to a propylene-olefin block copolymer and propylene homopolymer containing 50% by weight or more of propylene polymerized units, and the term "polyethylene" refers to ethylene alone. It means a polymer and an ethylene-α-olefin random copolymer containing 50% by weight or more of ethylene polymerized units.

As used herein, the term "polypropylene" refers to a propylene homopolymer and a propylene-olefin random copolymer and a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units, The term "polyethylene"
It means an ethylene homopolymer and an ethylene-olefin random copolymer containing 50% by weight or more of ethylene polymerized units.

The polyethylene constituting the component (a) of the polypropylene composition of the first invention has an intrinsic viscosity [η] of 15 to 100 dl measured in tetralin at 135 ° C.
/ G of polyethylene, an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units, preferably an ethylene homopolymer or an ethylene containing 70% by weight or more of ethylene polymerized units. Olefin copolymers, particularly preferably ethylene homopolymers or ethylene-olefin copolymers containing at least 90% by weight of ethylene polymer units, are suitable, and these (co) polymers are not only one type but also two types. The above may be mixed.

When the intrinsic viscosity [η] of the polyethylene (a) is less than 15 dl / g, the effect of improving the melt tension and crystallization temperature of the obtained polypropylene composition becomes insufficient, and the intrinsic viscosity [η] The upper limit of is not particularly limited, but if the difference from the intrinsic viscosity [η] of the polypropylene of the component (b) is large, when the composition is used as the component (b)
Dispersion of the polyethylene of the component (a) in the polypropylene of the component becomes poor, and as a result, the melt tension does not increase. Further, from the viewpoint of manufacturing efficiency, the upper limit is preferably set to about 100 dl / g. The intrinsic viscosity [η] of the component (a) polyethylene is 15 to 100 dl / g, preferably 17 to 5 dl / g.
The range is 0 dl / g. In addition, since the intrinsic viscosity [η] of the polyethylene of component (a) measured in tetralin at 135 ° C. must be increased to 15 dl / g, from the viewpoint of increasing the molecular weight, 5 units of ethylene polymerized units are required.
It is preferably at least 0% by weight.

The olefin other than ethylene copolymerized with the ethylene constituting the component (a) polyethylene is not particularly limited, but an olefin having 3 to 12 carbon atoms is preferably used. Specifically, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-octene,
1-decene, 4-methyl-1-pentene, 3-methyl-
Examples thereof include 1-pentene, and these olefins may be not only one kind but also two or more kinds.

The density of the polyethylene of the component (a) is not particularly limited, but specifically, 0.880 to 0.8.
Those having about 980 g / cm 3 are preferable.

The component (b) constituting the polypropylene composition of the present invention is a polypropylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units. It is a propylene-olefin block copolymer or a propylene homopolymer containing 50% by weight or more, and preferably an ethylene-olefin block copolymer containing a propylene polymerization unit content of 70% by weight or more. These (co) polymers may be not only one kind but also a mixture of two or more kinds.

The olefin other than propylene which is copolymerized with propylene constituting component (b) polypropylene is not particularly limited, but an olefin having 2 to 12 carbon atoms is preferably used. Specifically, ethylene, 1
-Butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like. It may be the above.

The polypropylene composition of the present invention is used in an amount of 0.01 to 5 parts by weight, preferably 0.10 to 2 parts by weight, particularly preferably 0.2 to 1 part by weight of the above-mentioned component (a).
Parts by weight and 100 parts by weight of the component (b) polypropylene. When the polyethylene of component (a) is less than 0.01 part by weight, the effect of improving the melt tension of the obtained polypropylene composition is low and the effect of improving the framing drip property during combustion is small, and when it exceeds 5 parts by weight, the effect is increased. Saturates, and the homogeneity of the obtained polypropylene composition may be impaired.

Further, the melt tension of the polypropylene composition is 1 to 20 cN, preferably 2 to 15 cN. If the melt tension is too large, the moldability and appearance of the final composition deteriorate, so that the melt tension is preferably 20 cN or less, and 1 cN or less. If it is smaller than the above, the flaming drip property during combustion increases remarkably, which is not preferable as the base resin of the flame-retardant resin composition of the present invention.

The melt tension (MS) was measured by using a melt tension tester type 2 manufactured by Toyo Seiki Seisaku-sho, Ltd., and heating the polypropylene composition to 230 ° C. in an apparatus. 2 from nozzle
It is a value (unit: cN) obtained by measuring the tension of the filamentous polypropylene composition when the strand is extruded into the air at 23 ° C. at a speed of 0 mm / min and taken up at a speed of 4.71 m / min.

The stereoregularity of the polypropylene composition of the present invention is not particularly limited, and any polypropylene that achieves the object of the present invention may be used as long as it is a crystalline polypropylene. Specifically, the isotactic pentad fraction (mmmm) measured by 13C-NMR (nuclear magnetic resonance spectrum) is 0.80 to 0.99, preferably 0.85 to 0.99, and particularly preferably 0.1 to 0.99. 90-0.
99 crystalline polypropylene composition.

Isotactic pentad fraction (mmm
m) is 13C-NM proposed by A. Zambelli et al. (Macromolecules 6, 925 (1973)).
R is the isotactic fraction in pentad units in the polypropylene molecular chain, which is measured by R.
(A. Zambelli) et al. (Macromolecules 8, 687
(1975)). In particular,
Using a mixed solution of o-dichlorobenzene / bromide benzene = 8/2 weight ratio with a polymer concentration of 20% by weight, 67.20.
It is determined by measuring at 130 MHz. As a measuring device, for example, JEOL-GX270
An NMR measurement device (manufactured by JEOL Ltd.) is used.

The method for producing the polypropylene composition (A) having the "basic constitution" is not limited to the production method as long as the melt tension of the composition satisfies the characteristics of the present invention. Can be easily produced by employing the method of the improved constitution 1 in which propylene or propylene and another olefin are main- (co) polymerized in the presence of a catalyst preactivated by the olefin.

That is, as a method for producing the polypropylene composition (A) having the basic structure, ethylene alone or in the presence of a catalyst used in the main polymerization of polyolefin, an olefin having 3 to 12 carbon atoms as a comonomer containing ethylene as a main component. Is activated by preliminary (co) polymerization of one or more of the above (pre-activation), and then can be obtained by main (co) polymerization of propylene alone or propylene and another olefin as a comonomer. The polymerization method can use a known catalyst and process.For example, a Ziegler-Natta type catalyst or a known reduction-type or supported-type high-activity catalyst or the like is used for slurry polymerization, solution polymerization or gas-phase polymerization. (Co) polymerization is possible, and the MFR [230 ° C .; 21.18 N] of the resulting polymer can be changed by adjusting the amount of addition in a known hydrogenation method.

As used herein, the term "pre-activation" refers to the high molecular weight activity of the catalyst for producing polyolefins, as measured by the propylene (propylene) or propylene and other olefins.
This means pre-activation prior to conducting the polymerization, and pre-activation (co) of ethylene or ethylene and other olefins in the presence of a polyolefin production catalyst.
It is carried out by polymerizing and supporting on a catalyst.

The preactivated catalyst used in the present improved configuration 1 is a catalyst component of a transition metal compound containing at least a titanium compound, and 0.01 to 1,000 per mole of transition metal atom.
Periodic Table of Mole (1991 version), Groups 1 and 2, 12
Metal compound [AL1] selected from the group consisting of metals belonging to Group 13 and Group 13, and 0 to 500 moles of an electron donor [Ed per mole of transition metal atom]
1], and an intrinsic viscosity [η] of less than 15 dl / g measured in tetraline at 135 ° C. of 0.01 to 100 g per 1 g of the transition metal compound component supported on the catalyst. Polypropylene (aP) for the purpose of main (co) polymerization, and 0.01 to 5,000 per gram of the transition metal compound catalyst component
g of intrinsic viscosity [η] measured in tetralin at 135 ° C.
Is 15 to 100 dl / g.

In the preactivated catalyst, any known catalyst component mainly composed of a transition metal compound catalyst component containing at least a titanium compound proposed for polyolefin production is used as the transition metal compound catalyst component. Among them, a titanium-containing solid catalyst is preferably used for industrial production.

As the titanium-containing solid catalyst component, a titanium-containing solid catalyst component containing a titanium trichloride composition as a main component (JP-B-56-3356, JP-B-59-2857)
No. 3, JP-B-63-66323, etc.) and a titanium-containing supported catalyst component containing titanium tetrachloride as a magnesium compound and having titanium, magnesium, halogen and an electron donor as essential components (Japanese Patent Application Laid-Open No. Sho 63-66323). 62-10481
0, Japanese Patent Application Laid-Open No. 62-104811, Japanese Patent Application Laid-Open
JP-A-2-104812, JP-A-57-63310, JP-A-57-63311, JP-A-58-830
No. 06, Japanese Patent Application Laid-Open No. 58-138712, etc.), and any of these can be used.

As the organometallic compound [AL1], the first, second, twelfth and twelfth groups of the Periodic Table (1991 edition) can be used.
A compound having an organic group of a metal selected from the group consisting of metals belonging to Group 3, such as an organolithium compound, an organosodium compound, an organomagnesium compound, an organozinc compound, an organoaluminum compound, and the like; Can be used in combination with

In particular, when the general formula is AlR ¹ _p R ² _q X
_{3- (p + q)} (wherein, R ¹ and R ² are the same or different of a hydrocarbon group such as an alkyl group, a cycloalkyl group and an aryl group and an alkoxy group, X represents a halogen atom,
p and q represent a positive number of 0 <p + q ≦ 3), and an organoaluminum compound represented by the following formula (1) can be preferably used.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-aluminum. Hexyl aluminum, trialkyl aluminum such as tri-n-octyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-i
-Dialkylaluminum monohalides such as butylaluminum chloride, diethylaluminum bromide and diethylaluminum iodide; dialkylaluminum hydrides such as diethylaluminum hydride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; monoalkylaluminum dihalides such as ethylaluminum dichloride. Other examples include alkoxyalkylaluminums such as diethoxymonoethylaluminum. Preferably, trialkylaluminum and dialkylaluminum monohalide are used. These organoaluminum compounds can be used alone or in combination of two or more.

The electron donor [Ed1] is used as needed for the purpose of controlling the production rate and / or stereoregularity of the polyolefin. Electron donor [Ed
1] includes, for example, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, ureas and thioureas, isocyanates, azo compounds, phosphines, phosphites , Phosphinite, hydrogen sulfide and organic compounds having any atom of oxygen, nitrogen, sulfur or phosphorus in the molecule such as thioethers, neoalcohols, silanols, etc. and having Si-OC bond in the molecule And organic silicon compounds.

As ethers, dimethyl ether,
Diethyl ether, di-n-propyl ether, di-n
-Butyl ether, di-i-amyl ether, di-n-
Pentyl ether, di-n-hexyl ether, di-i
-Hexyl ether, di-n-octyl ether, di-i
-Octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like, alcohols such as methanol,
Ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, etc., and phenols such as phenol, cresol, xylenol, ethyl phenol, naphthol, etc. .

Examples of the esters include methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, butyl formate, amyl acetate, and n-butyl acetate. Octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, methyl anisate, Monocarboxylic acid esters such as ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, and ethyl phenylacetate , Diethyl succinate, methyl malonate Aliphatic polycarboxylic acid esters such as butyl, diethyl butylmalonate, dibutyl maleate and diethyl butylmaleate, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate and mono-phthalate. n-butyl, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl i-phthalate, i-
Dipropyl phthalate, dibutyl i-phthalate, di-2-ethylhexyl i-phthalate, diethyl terephthalate,
Aromatic polycarboxylic acid esters such as dipropyl terephthalate, dibutyl terephthalate, and di-i-butyl naphthalenedicarboxylate are exemplified.

The aldehydes include acetaldehyde, propionaldehyde, benzaldehyde and the like, and the carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid,
Monocarboxylic acids such as oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, and benzoic acid and acid anhydrides such as benzoic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride are used as acetone, Methyl ethyl ketone,
Examples thereof include methyl-i-butyl ketone and benzophenone.

Examples of the nitrogen-containing compound include nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, , 4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine,
2,2,5,5, tetramethylpyrrolidine, N, N,
Amines such as N ′, N′-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′,
Amides such as N ″ -pentamethyl-N′-β-dimethylaminomethylphosphoric acid triamide, octamethylpyrophosphoramide, ureas such as N, N, N ′, N′-tetramethylurea, phenylisocyanate, toluyl Examples include isocyanates such as isocyanate and azo compounds such as azobenzene.

Examples of the phosphorus-containing compound include phosphines such as ethyl phosphine, triethyl phosphine, tri-n-octyl phosphine, triphenyl phosphine, and triphenyl phosphine oxide; dimethyl phosphite;
Phosphines such as di-n-octylphosphine, triphenylphosphine and triphenylphosphine oxide, dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite and triphenyl phosphite; Phosphites are exemplified.

Examples of the sulfur-containing compound include thioethers such as diethylthioether, diphenylthioether and methylphenylthioether, ethylthioalcohol,
thioalcohols such as n-propylthioalcohol and thiophenol; and further, as an organosilicon compound, trimethylsilanol, triethylsilanol,
Silanols such as triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, -I-propyldimethoxysilane, di-i-butyldimethoxysilane, diphenyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane , Vinyltriacetoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxy Silane, cyclohexyl methyl dimethoxy silane, cyclohexyl trimethoxy silane, dicyclohexyl dimethoxysilane, in the molecule such as 2-norbornyl methyl dimethoxy silane Si-O-C
An organic silicon compound having a bond may be used. These electron donors can be used alone or as a mixture of two or more.

In the preactivated catalyst, the polyethylene (aE) has an intrinsic viscosity [η] of 15 to 100 dl / g, preferably 17 to 5 in tetralin at 135 ° C.
Ethylene homopolymer in the range of 0 dl / g or a copolymer of ethylene and an olefin having 3 to 12 carbon atoms having an ethylene polymerized unit content of 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or less. And finally constitutes the polyethylene of the component (a) of the polypropylene composition having the basic structure. Therefore, the intrinsic viscosity [η1] of the polyethylene component (a) of the basic constitution and the intrinsic viscosity [η2] of the polyethylene (aE) of the improved constitution 1 are as follows:
[Η1] = [η2].

The supported amount of polyethylene (aE) per 1 g of the transition metal compound catalyst component is 0.01 to 5,000 g,
Preferably it is 0.05-2,000 g, more preferably 0.1-1,000 g. When the amount supported per 1 g of the transition metal compound catalyst component is less than 0.01 g, the effect of improving the melt tension and crystallization temperature of the polypropylene composition finally obtained by the (co) polymerization is insufficient.
If it exceeds 000 g, not only the improvement of those effects will not be remarkable, but also the homogeneity of the finally obtained polypropylene composition may deteriorate, which is not preferable.

On the other hand, polypropylene (aP)
The intrinsic viscosity [η] measured in tetralin at 15 ° C. is 15 dl
/ G is a polypropylene having the same composition as the component (b) polypropylene for the purpose of main (co) polymerization, and is finally incorporated as a part of the component (b) polypropylene in the basic polypropylene composition. Polypropylene (a-P) is a component that imparts dispersibility of polyethylene (aE) to the finally obtained polypropylene composition, and in that sense, its intrinsic viscosity [η] is higher than that of polyethylene (aE). It is preferably smaller than the intrinsic viscosity [η] and larger than the intrinsic viscosity [η] of the finally obtained polypropylene composition.

On the other hand, the supported amount of polypropylene (aP) per 1 g of the transition metal compound catalyst component is 0.01 to 100.
g, in other words, the range of 0.001 to 1% by weight based on the finally obtained polypropylene composition is suitable. If the supported amount of polypropylene (aP) is small, the dispersibility of polyethylene (aE) in the target polypropylene composition becomes insufficient, and if it is too large, polyethylene (aE)
Not only saturates the effect on the polypropylene composition, but also lowers the production efficiency of the preactivated catalyst.

In this improved configuration, the preactivated catalyst is
In the presence of a catalyst for polyolefin production comprising a combination of a catalyst component of a transition metal compound containing at least a titanium compound, an organometallic compound [AL1] and an electron donor [Ed1] used as desired, Preliminary (co) polymerization of propylene or propylene with other olefins to produce polypropylene (aP), and then preactivated (co) polymerization of ethylene or ethylene and other olefins with polyethylene (aE)
Is produced, and the transition metal compound catalyst component is produced by a preactivation treatment in which polypropylene (aP) and polyethylene (aE) are supported.

In this preactivation treatment, the transition metal compound catalyst component containing a titanium compound, and 0.01 to 1,000 mol, preferably 0.05 to 500 mol, of the organic metal are added to 1 mol of the transition metal in the catalyst component. 0 to 500 mol, preferably 0 to 100 mol, of the electron donor [Ed1] based on 1 mol of the transition metal in the compound [AL1] and the catalyst component
And used as a catalyst for polyolefin production.

The polyolefin-producing catalyst is used in an amount of 0.001 to 5,000 mmol, preferably 0 to 5,000 mmol, as the transition metal atom in the catalyst component, per liter of the (co) polymerization volume of ethylene or ethylene and other olefins. .
Propylene or a mixture of propylene and propylene with another olefin for the purpose of (co) polymerization in the presence of from 0.01 to 1,000 mmol and in the absence of a solvent or in a solvent up to 100 liters per gram of the transition metal compound catalyst component.
Of the transition metal compound catalyst component to produce 0.01 to 100 g of polypropylene (aP) per 1 g of the transition metal compound catalyst component, and then ethylene or a mixture of ethylene and ethylene and other olefins. 0.01 g to 10,000 g, and pre-activated (co) polymerized to produce 0.01 to 5,000 g of polyethylene (aE) per 1 g of the transition metal compound catalyst component. Is coated with polypropylene (a-P) and polyethylene (aE). In the present specification, the term `` polymerization volume '' means the volume of the liquid phase portion in the polymerization vessel in the case of liquid phase polymerization, and the volume of the gas phase portion in the polymerization vessel in the case of gas phase polymerization. I do.

The amount of the transition metal compound catalyst component used is preferably in the above range in order to maintain an efficient and controlled (co) polymerization reaction rate of propylene. Also,
If the amount of the organometallic compound [AL1] is too small, the (co) polymerization reaction rate will be too slow. This is not preferred because the amount of the organometallic compound [AL1] remaining in the resulting polypropylene composition increases. Further, if the amount of the electron donor [Ed1] is too large, the (co) polymerization reaction rate is reduced. If the amount of the solvent used is too large, not only a large reaction vessel is required, but also it is difficult to efficiently control and maintain the (co) polymerization reaction rate.

The preactivation treatment includes, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, isooctane, decane and dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; It can be performed in a liquid phase using an aromatic hydrocarbon such as xylene or ethylbenzene, an inert solvent such as a gasoline fraction or a hydrogenated diesel oil fraction, or an olefin itself. It is also possible to do it in phase.

The preactivation treatment may be carried out in the presence of hydrogen, but the intrinsic viscosity [η] is 15 to 100 d.
In order to produce 1 / g high molecular weight polyethylene (aE), it is preferable not to use hydrogen.

In the preactivation treatment, the conditions for the preliminary (co) polymerization of propylene or a mixture of propylene and other olefins for the purpose of (co) polymerization are as follows: polypropylene is used in an amount of 0.01 g to 10 g per 1 g of the transition metal compound catalyst component.
Any condition can be used as long as it produces 0 g.
At a temperature of 0 ° C. and a pressure of 0.1 MPa to 5 MPa, 1
Run for minutes to 24 hours. The preactivation (co) polymerization conditions for ethylene or a mixture of ethylene and another olefin are as follows: polyethylene ((aE) is used in an amount of 0.01 to 5,000 g, preferably 0.05 to 2 g, per gram of the transition metal compound catalyst component. 000 g, more preferably 0.1 to
There is no particular limitation as long as the condition is such that it is produced in an amount of 1,000 g.
0.1 MPa to 5 MPa, preferably 0.2 MPa to 5 MPa, particularly preferably 0.3 MPa at a relatively low temperature of about 30 ° C. to 30 ° C., more preferably about −40 ° C. to 20 ° C.
1 minute to 24 hours under a pressure of ５5 MPa, preferably 5
Minutes to 18 hours, particularly preferably 10 minutes to 12 hours.

Further, after the preactivation treatment, propylene or a mixture of propylene and other olefins for the purpose of main (co) polymerization is used for the purpose of suppressing a decrease in main (co) polymerization activity due to the preactivation process. By addition of from 0.01 to 10 per gram of the transition metal compound catalyst component.
The reaction may be performed with a reaction amount of 0 g of polypropylene. In this case, the organometallic compound [AL1], the electron donor [Ed]
1], the solvent, and the amount of propylene or a mixture of propylene and other olefins can be used in the same range as in the preactivated polymerization using ethylene or a mixture of ethylene and other olefins. 0.005 to 10 mol, preferably 0.1 to 10 mol per mol.
It is preferably carried out in the presence of from 01 to 5 mol of electron donor. The reaction is carried out at a temperature of -40 to 100 ° C and a pressure of 0.1 to 5 MPa for 1 minute to 24 hours.

The organometallic compound [A] used for the addition polymerization
L1], the electron donor [Ed1], and the type of the solvent may be the same as those used in the preactivated polymerization using ethylene or a mixture of ethylene and another olefin.
For propylene or a mixture of propylene and other olefins, one having the same composition as for the purpose of the present (co) polymerization is used. The intrinsic viscosity [η] of polypropylene produced by addition polymerization is the intrinsic viscosity [η] of polyethylene (aE).
It is a smaller range and is finally incorporated as a part of the polypropylene of the component (b) after the main (co) polymerization.

The preactivated catalyst can be used as such or with an additional organometallic compound [AL2] and an electron donor [Ed2].
As an olefin main (co) polymerization catalyst further containing
To 12 olefins for the main (co) polymerization.

The above-mentioned olefin main (co) polymerization catalyst comprises the above-mentioned preactivation catalyst and one or more transition metal atoms in the preactivation catalyst.
Total [AL1 + AL2] of the organometallic compound [AL2] and the organometallic compound [AL1] in the activation catalyst per mole
0.05 to 3,000 mol, preferably 0.1 to 1,
The electron donor [Ed2] is added to the total of [Ed1 + Ed2] of the pre-activated catalyst with respect to 000 mol and 1 mol of the transition metal atom in the activation catalyst, and 0 to 5,
000 mol, preferably from 0 to 3,000 mol.

The content of the organometallic compound [AL1 + AL
If 2] is too small, the (co) polymerization reaction rate in the main (co) polymerization of propylene or propylene and other olefins is too slow. No increase is observed, which is not only inefficient, but also undesirably, because the organometallic compound residue remaining in the finally obtained polypropylene composition increases. Further, the content of the electron donor [Ed1 + E
When [d2] is excessively large, the (co) polymerization reaction rate is significantly reduced.

The types of the organometallic compound [AL2] and the electron donor [Ed2] additionally used as necessary in the olefin main (co) polymerization catalyst are described above with respect to the organometallic compound [AL1] and the electron donor. The same one as [Ed1] can be used. One type may be used alone, or two or more types may be used in combination. Further, they may be the same or different from those used in the pre-activation treatment.

The catalyst for the olefin main (co) polymerization may be a solvent, an unreacted olefin,
Organometallic compound [AL1] and electron donor [Ed]
1] or the like by filtration or decantation and removal, or a suspension obtained by adding a solvent to the granules, an additional organometallic compound [AL2] and, if desired, an electron donor [ Ed2], and
The solvent and the unreacted olefin present are removed by distillation under reduced pressure or by evaporating with an inert gas stream or the like. ] And an electron donor [Ed2].

In the method for producing a polypropylene composition of the present Improved Configuration 1, the amount of the preactivated catalyst or the catalyst for olefin main (co) polymerization is as follows: per 1 liter of the polymerization volume, the transition metal atom in the preactivated catalyst. Converted to
0.001 to 1,000 mmol, preferably 0.00
Use 5-500 mmol. By setting the amount of the transition metal compound catalyst component in the above range, it is possible to maintain an efficient and controlled (co) polymerization reaction rate of propylene or a mixture of propylene and a composition olefin.

The main (co) polymerization of propylene or a mixture of propylene and another olefin in the present improved constitution 1 is performed by a known olefin (co) polymerization process.
Polymerization processes can be used, and specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, isooctane, decane, dodecane, and cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane. A slurry polymerization method that carries out (co) polymerization of olefins in an aromatic hydrocarbon such as hydrogen, toluene, xylene, ethylbenzene, or an inert solvent such as a gasoline fraction or hydrogenated diesel oil fraction. Bulk polymerization method used as solvent, olefin (co)
A gas phase polymerization method in which the polymerization is carried out in a gas phase, a liquid phase polymerization in which a polyolefin produced by (co) polymerization is in a liquid state, or a polymerization process combining two or more of these processes can be used.

In the case of using any of the above polymerization processes, the polymerization conditions include a polymerization temperature of 20 to 120 ° C., preferably 30 to 100 ° C., and particularly preferably 40 to 100 ° C.
° C, the polymerization pressure is 0.1 to 5 MPa, preferably in the range of 0.3 to 5 MPa, continuous, semi-continuous,
Alternatively, the polymerization time in the range of about 5 minutes to 24 hours is employed in a batch manner. By adopting the above polymerization conditions, the polypropylene as the component (b) can be produced with high efficiency and a controlled reaction rate.

In a more preferred embodiment according to the method for producing the polypropylene composition (A) of the present constitution, the polypropylene of the (aP) component produced in the (co) polymerization and the MFR [230] of the finally obtained polypropylene composition
C .; 21.18 N] is 0.1 to 50 g / 10 min, preferably 0.3 to 30 g / 10 min, and more preferably 0.3 to 30 g / 10 min.
-20 g / 10 min, and in the obtained polypropylene composition, the polyethylene (aE) derived from the preactivated catalyst used is 0.01 to 5% by weight, preferably 0.1 to 2% by weight. The polymerization conditions are selected so as to be in the range of 0.2 to 1% by weight. Further, similarly to the known olefin polymerization method, the MFR of the (co) polymer obtained by using hydrogen during the polymerization can be adjusted.

After the completion of the (co) polymerization, if necessary, a post-treatment step such as a known catalyst deactivation treatment step, catalyst residue removal step, drying step, etc. is carried out to obtain the desired high melt tension and high crystallization temperature. Is finally obtained.

In the method for producing a polypropylene composition of the present improved structure 1, a method is employed in which high-molecular-weight polyethylene (aE) is produced by a preactivation step and is uniformly dispersed in the finally obtained polypropylene composition. Therefore, the required amount of the preactivation catalyst can be adjusted collectively, while the main (co) polymerization of propylene or propylene and other olefins uses the existing process to carry out ordinary olefin (co) polymerization. Since it suffices to carry out the production, it is possible to maintain a production amount equivalent to that of ordinary production of polyolefin.

By adopting the method for producing a polypropylene composition using the preactivated catalyst of the present improved constitution 1, the melt tension (MS) at 230 ° C. and the MF
A crystalline polypropylene composition satisfying R [230 ° C .; 21.18 N], density and melting point can be easily obtained.

The polypropylene composition of the present invention contains 50% by weight of a propylene homopolymer or a propylene polymer unit.
It is a propylene-olefin block copolymer containing at least 70% by weight of propylene polymerized units, more preferably 80% by weight or more of propylene polymerized units. These (co) polymers may be not only one kind but also a mixture of two or more kinds.

The polypropylene composition of this constitution contains 0.01 to 5 parts by weight of the polyethylene of the component (a) and has an MF
R [230 ° C .; 21.18N] is 0.1 to 50 g / 10 mi
n, preferably 0.3 to 30 g / 10 min, more preferably 0.3 to 20 g / 10 min and a density of 0.1 to 0.3 g / min.
890-0.910 g / cm ³ , crystal melting point (Tm) 1
It is a crystalline polypropylene of 50 to 167 ° C. Also,
The composition can use not only a propylene homopolymer but also a propylene-olefin block copolymer containing 50% by weight or more of propylene polymerized units, and preferably has a propylene polymerized unit content of 70% by weight or more, More preferably, a propylene-ethylene block copolymer having a propylene polymerization unit content of 80% by weight or more is suitable. These (co) polymers can be used alone or in combination of two or more. is there.

The halogen-based flame retardant used in the flame-retardant polyolefin composition of the present invention includes ammonium bromide,
Ammonium chloride, 2-chlorotetrabromobutane, 2,2-
Bis [p- (chloroformyloxy) phenyl-3] propane, 1,2-dibromo-3-chloropropane, 1,2,3-tribromopropane, 1,1,2,2-tetrabromoethane, tetrabromobutane , Hexabromocyclododecane, hexabromooctane, hexabromobutane, pentabromocyclohexane, tribromotrichlorocyclohexane, pentabromochlorocyclohexane, 1,2-dibromo-1,1,2,2-
Tetrachloroethane, 2,2-bis (4-hydroxyethoxy
-3,5-dibromophenyl) propane, vinyl chloroacetate, 2,4,6-tribromophenyl methacrylate,
3,3'-tribromoallylformate, 2,2-dibromopropyl methacrylate, bis (2,3-dibromopropyl)-
2,3-dibromofumarate, tribromophenyl acrylate, chloroendic acid, diallyl chloroendate, chloroendic anhydride, bromostyrene, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chloropropanediol, 3-bromo-2, 2-bis (bromomethyl) propanol, 2,2-dibromobutene-1,4-diol, tribromophenol, dibromoneopentyl glycol, tribromoneopentyl alcohol, 2,3-dibromopropanol, 2,3,3'- Tribromoallyl alcohol, chloropentabromophenyl allyl ether, pentachlorophenoxyglycerin ether, bromophenyl allyl ether, tribromophenol allyl ether, pentabromophenol allyl ether, pentabromophenyl allyl ether, bromoalkenyl Ethers, sorbitol-1,6-bis (2', 3'-dibromopropyl) ether,
Decabromobiphenyl, decabromodiphenyl ether, decabromodiphenyl ketone, decabromodiphenyl carbonate, decabromodiphenyl sulfide, decabromodiphenyl disulfide, decabromodiphenylsulfone, decabromodiphenylmethane, 1,2-bis (2 ′, 3 ′, 4 ', 5', 6'-pentabromophenoxy) ethane, 1,2-bis (2 ', 3', 4 ', 5', 6'-pentabromophenyl) ethane, 1,1-bis (2 ', 3 ', 4', 5 ', 6'-pentabromophenyl) ethane, 2,2-bis (2', 3 ', 4', 5 ',
6'-pentabromophenyl) propane, pentadecabromotriphenylamine, pentadecabromotriphenylphosphine, hexabromodiphenyl ether, dibromocresyl glycidyl ether, pentabromoallyl ether, 1,2-dibromopropyl-tribromophenyl ether , Decachlorodiphenyl carbonate, decabromodiphenyl carbonate, 2,3,3-tribromoallylcarboxylate, 2,3,5,6,2 ', 3', 5 ', 6'-octachloro-4,4'- Dioxydiphenyl, tetrabromobenzene, α, β-dibromoethylbenzene, 2-bromo-α, β-
Dibromoethylbenzene, hexabromobenzene, perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, N, N'-ethylene-bis (dibromophthalimide), N, N'-methylene -Bis (tetrabromophthalimide), N, N'-ethylene-bis (tetrabromophthalimide), N, N'-ethylidene
-Bis (tetrabromophthalimide), N, N '-(1,3-
Propylene) -bis (tetrabromophthalimide), N,
N '-(1,2-propylene) -bis (tetrabromophthalimide), N, N'-(2,2-propylene) -bis (tetrabromophthalimide), N, N '-(1,4-butylene) -Bis (tetrabromophthalimide), N, N '-(1,6-hexamethylene) -bis (tetrabromophthalimide), N, N
'-(1,8-octamethylene) -bis (tetrabromophthalimide), N, N'-(2,5-dimethyl-2,5-hexamethylene) -bis (tetrabromophthalimide), N, N'-
(1,4-phenylene) -bis (tetrabromophthalimide), N, N '-(4,4'-biphenylene) -bis (tetrabromophthalimide), N, N'-(4,4 "-terphenylene) -Bis (tetrabromophthalimide), N, N'-methylene-bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N'-ethylene-bis (5,6-dibromonorbornane-2) , 3-dicarboximide), N, N'-ethylidene-bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N '-(1,3-propylene) -bis (5, 6-dibromonorbornane-2,3-dicarboximide), N, N '
-(1,2-propylene) -bis (5,6-dibromonorbornane
-2,3-dicarboximide), N, N '-(2,2-propylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N'-(1,4 -Butylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N'-
(1,6-hexamethylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N '-(1,8-octamethylene) -bis (5,6-dibromonorbornane- 2,3-dicarboximide), N, N '-(2,5-dimethyl-2,5-hexamethylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N '-(1,4-phenylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N'-(4,4'-biphenylene) -bis (5,6-dibromonorbornane) -2,3-dicarboximide), N, N '
-(4,4 "-terphenylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N'-methylene-bis (5,6-dibromo-1,4-epoxycyclohexane -2,3-dicarboximide), N, N'-ethylene-bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'-ethylidene-bis ( 5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N
'-(1,3-propylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'
-(1,2-propylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'-
(2,2-propylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'-
(1,4-butylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N ′-(1,6
-Hexamethylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'-
(1,8-octamethylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '
-(2,5-dimethyl-2,5-hexamethylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '-(1,4- Phenylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '-(4,4'-biphenylene) -bis (5,6-dibromo-1) , 4-Epoxycyclohexane-2,3-dicarboximide), N, N '-(4,4 "-terphenylene) -bis (5,6-
Dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '-(4,4'-biphenylsulfone)-
Bis (tetrabromophthalimide), N, N '-[4,4'-
Bis (3,5-dibromophenyl) sulfone] -bis (tetrabromophthalimide), N, N '-[4,4'-bis (2,
3,5,6-tetrabromophenyl) sulfone] -bis (tetrabromophthalimide), N, N '-(4,4'-biphenylmethane) -bis (tetrabromophthalimide), N, N
'-[4,4'-bis (3,5-dibromophenyl) methane] -bis (tetrabromophthalimide), N, N'-[4,4'-bis (2,3,5,6-tetrabromo) Phenyl) methane] -bis (tetrabromophthalimide), N, N '-[4,4'-biphenyl- (1,2-ethane)]-bis (tetrabromophthalimide), N, N'-[4,4 '-Bis (3,5-dibromophenyl)-(1,2-ethane)]-bis (tetrabromophthalimide), N, N'-[4,4'-bis (2,3,5,6-tetra) Bromophenyl)-(1,2-ethane)]-bis (tetrabromophthalimide), N, N '-[4,4'-biphenyl- (2,2'-propane)]-bis (tetrabromophthalimide), N, N '
-[4,4'-bis (3,5-dibromophenyl)-(2,2'-propane)]-bis (tetrabromophthalimide), N, N '
-[4,4'-bis (2,3,5,6-tetrabromophenyl)-(2,
2'-propane)]-bis (tetrabromophthalimide), poly (dibromostyrene), poly (tribromostyrene), poly (tetrabromostyrene), poly (pentabromostyrene), 1,4-bis (2 ', 3´, 4´, 5´, 6´-
Pentabromophenoxy) -2,3,5,6-tetrabromobenzene, 1,4-bis (2 ', 3', 4 ', 5', 6'-pentabromobenzyl) -2,3,5,6 -Tetrabromobenzene, 4,4'-bis (2,3,4,5,6-pentabromophenoxy) -2,2 ', 3,3',
5,5 ', 6,6'-octabromodiphenyl ether, 4,4'-
Bis (2,3,4,5,6-pentabromobenzyl) -2,2 ', 3,3
', 5,5', 6,6'-octabromodiphenylmethane, tetrabromobisphenol A, tetrabromobisphenol A diethoxylate, bis (2-hydroxyethyl ether) tetrabromobisphenol A, 2,2-bis [[3 ,
5-dibromo-4- (2 ', 3'-dibromopropyloxy)]
Phenyl] propane, 2,2-bis [[3,5-dibromo-4- (2
', 3'-Dibromo-2'-methylpropyloxy)] phenyl] propane, tetrabromobisphenol F, bis [[3,5-dibromo-4- (2', 3'-dibromopropyloxy)] phenyl] methane , Bis [[3,5-dibromo-4- (2
', 3'-dibromo-2'-methylpropyloxy)] phenyl] methane, bis [[3,5-dibromo-4- (2', 3'-dibromopropyloxy)] phenyl] oxide, bis [[3 , 5-Dibromo-4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] oxide, bis [[3,5-
Dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] ketone, bis [[3,5-dibromo-4- (2', 3'-
Dibromo-2'-methylpropyloxy)] phenyl] ketone, bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfide, bis [[3,
5-dibromo-4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] sulfide, tetrabromobisphenol S, bis [[3,5-dibromo-4- (2', 3'- Dibromopropyloxy)] phenyl] sulfone, bis [[3,5-dibromo-4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] sulfone, pentabromotoluene, tribromoaniline, acetylene Tetrabromide, 1- (p-tosyl) -3- (2'-bromo-4 ', 4', 4'-trichlorobutyl) urea, 2,3-dibromopropanol ester, chlorinated paraffin, chlorinated polyethylene or chlorine And inorganic and organic halogen-based flame retardants such as fluorinated polypropylene, and particularly, decabromodiphenyl ether, 1,2-bis (2 ′, 3 ′, 4 ′, 5 ′, 6′-pentabromophenyl) ethane, N, N 'ethylene-bis (tetrabromo cover Imide), perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A, tetrabromobisphenol S, 2,2-bis [[3,5-dibromo- 4- (2´, 3´
-Dibromopropyloxy)] phenyl] propane and bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone are preferred. These halogen-based flame retardants can be used alone, or two or more halogen-based flame retardants can be used in combination. The blending ratio of the halogen-based flame retardant is not particularly limited as long as it is blended according to the intended flame retardancy, but is usually 4 to 50% by weight, preferably 5 to 50% by weight, based on 100 parts by weight of the polyolefin.
-30 parts by weight.

The composition of the present invention may further contain a flame retardant auxiliary. Examples of the flame retardant aid include antimony compounds (for example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate,
Antimony trichloride, antimony trisulfide, antimony oxychloride, antimony dichloride perchloropentane and potassium antimonate), boron compounds (such as zinc metaborate, zinc tetraborate, zinc borate and basic zinc borate), Zirconium oxide, tin oxide, molybdenum oxide, and the like can be exemplified. Antimony trioxide, antimony tetroxide, antimony pentoxide, antimony trichloride, antimony trisulfide, and zinc borate are particularly preferable. Not only can these flame retardants be used alone, but also
More than one kind of flame retardant aid can be used in combination. The blending ratio of these flame retardants is not particularly limited, but is preferably 20 to 60 parts by weight based on 100 parts by weight of the halogen-based flame retardant. Since the compounding of the flame retardant aid acts synergistically with the halogen-based flame retardant in the composition of the present invention to increase the flame retardancy, the compounding amount of the halogen-based flame retardant can be reduced. Therefore, the blending of the flame retardant auxiliary is preferable.

For the flame-retardant polyolefin compositions (C), (D) and (E) of the present invention, the bis (2,2,2) 6-di-tert-butyl-4-methylphenyl)
Pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t) Phosphorus antioxidants, such as 2-butylphenyl) phosphite and tetrakis (2,4-ditert-butylphenyl) 4,4'-biphenylenediphosphite, 2.6-di-t-butyl
-P-cresol, tetrakis [methylene (3,5-di-t-
Butyl-4-hydroxyhydrocinnamate)] methane,
1,3,5-trimethyl-2,4,6-tris (3,5-di-t-
Phenolic antioxidants such as butyl-4-hydroxybenzyl) benzene and tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate; di-stearyl-ββ′-thio-di-propionate; -Myristil-
ββ'-thio-di-propionate, di-lauryl-ββ'-
Thio-antioxidants such as thio-di-propionate, neutralizing agents such as calcium stearate, hydrotalcite (trade name: Kyowa Chemical Industry), 2-hydroxy-4-n-octoxybenzophenone, 2- (2 'Hydroxy-3', 5'-di
-t-butylphenyl) -5-chlorobenzotriazole,
UV absorbers such as 2- (2'hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate 2,4-di-t-butylphenyl-3 ', 5
'-Di-t-butyl-4'-hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, dimethyl succinate 2- (4-hydroxy-2,2,6) , 6
-Tetramethyl-1-peripyridyl) ethanol condensate,
Poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2,
6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N'-bis (3-aminopropyl)
Ethylenediamine-2,4-bis [N-butyl-N- (1,2,
2,6,6-pentamethyl-4-piperidyl) amino] -6-
An optional amount of a light stabilizer such as a chloro-1,3,5-triazine condensate can be added.

Further, the inorganic filler is improved in physical properties, for example, rigidity,
It is used in accordance with required characteristics such as creep characteristics, molding shrinkage, appearance, and the like.Examples include talc, calcium carbonate, titanium potassium whisker, glass fiber, mica, magnesium hydroxide, silica, zeolite, sericite, and the like. May be used alone or in combination. Talc has a specific surface area of 17,000 cm ² / g or more and an average particle diameter of 20 μm or less, preferably 5 μm or less, more preferably 2 μm or less.
A talc having a particle size of 10 μm or less and a particle size exceeding 10 μm is 5% by weight or less, preferably 1% by weight or less in terms of impact resistance. Calcium carbonate has a specific surface area of 8.0
100 cm ² / g or more, average particle size of 3 μm or less and 10 μm
Those having 5% by weight or less of a particle size component exceeding m can be exemplified. Examples of the potassium titanate whiskers include whiskers having an average fiber diameter of 0.2 to 1.5 μm and an average fiber length of 10 to 50 μm. Examples of mica include mica having an average flake diameter of 200 to 40 μm and an aspect ratio of 30 to 70. Examples of the glass fiber include glass fibers having an average fiber length of 4 to 13 μm and a fiber length of 3 to 6 mm. Magnesium hydroxide has an average particle size of 0.5 to 2 μm, and zeolite has an average particle size of 10 to 2 μm.
0 μm, 3 to 10 μm for sericite, and 1 to 15 μm for the silica. Further, examples of the filler include an untreated filler and a filler which has been subjected to silane treatment to increase the reinforcing effect. In addition, a metal deactivator (copper damage inhibitor), an antistatic agent, a colorant and a dispersant such as a wax or a fatty acid metal salt for dispersing the colorant, a crystal nucleating agent, and a general polypropylene (random copolymer and block) (Copolymer), polyethylene, olefin-based elastomer and the like can be blended within a range that does not impair the object of the present invention.

The flame-retardant polyolefin compositions (C), (D), (E), (F) and (G) of the present invention can be obtained by mixing the above components. To mix these components,
For example, a mixer with a high-speed stirrer such as a Henschel mixer (trade name) or a super mixer (trade name), or a usual mixing device such as a ribbon blender or a tumbler may be used. When melt kneading is required, it can be obtained by pelletizing with a usual single screw extruder or twin screw extruder. The kneading temperature is generally 190 to 250 ° C. However, depending on the flame retardant, the temperature is limited to the decomposition temperature, and the kneading temperature is preferably set to about 190 to 210 ° C.

As a method for obtaining a molded article using the flame-retardant polyolefin composition of the present invention, it is important to select a molding temperature in consideration of the decomposition temperature of the flame retardant so as not to impair the flame retardancy. is there. Generally 190-250
Examples include an injection molding machine and an extruder set at a temperature of ° C. In addition,
For injection molding, MFR (230 ° C; 21.18N) is 3 ~
Materials with 50 g / 10 min, preferably 5-20 g / 10 min, more preferably 8-15 g / 10 min are preferred. When extrusion molding is used to form a hollow molded article or sheet, the MFR (23
0 ° C; 21.18N) is 0.1 to 4 g / 10min, preferably 0.3 to 10 g / min.
It is preferred to use 3 g / 10 min of the flame-retardant polyolefin composition of the invention.

[0079]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited by these specific examples. The following methods were used to evaluate the characteristics used in the following examples and comparative examples. (1) Crystal melting point (abbreviation: Tm): A 10 mg sample was measured from a room temperature (23 ° C.) at a heating rate of 20 ° C./min under a nitrogen atmosphere using a scanning differential calorimeter (abbreviation: DSC). It is expressed as the peak temperature of the endothermic curve (unit: ° C) accompanying the melting of. (2) Density: Measured based on JIS K7112 (1980) test condition D method (density gradient tube method) (unit: g / c)
m ^3). (3) Specific gravity: Measured based on JIS K7112 (1980) test condition A method (water substitution method). (4) MFR-II: Test condition 14 of JIS K7210
(230 ° C; 21.18N) (unit: g / 10mi)
n). (5) MFR-II: Test condition 4 of JIS K7210
(190 ° C; 21.18N) (unit: g / 10mi)
n). (6) Intrinsic viscosity [η]: The viscosity determined when the polymer is in an extremely diluted state in a given solvent at a temperature determined for the polymer. In the case of the present invention, the viscosity was determined at 135 ° C. using tetralin (tetrahydronaphthalene) as a solvent and using an automatic viscosity meter AVS2 manufactured by Mitsui Toatsu Co. (unit: dl / g). (8) Flame retardancy: 127 × 1 prepared by injection molding
Using a 2.7 × 0.8 mm test piece, a test is performed in accordance with the UL94 vertical fire test method, which is a UL standard in the United States, to evaluate the flame retardancy (class). (9) Cotton ignitability: Evaluate the presence or absence of igniting of absorbent cotton immediately below the test piece where resin melted and dropped by burning in the UL94 vertical burning test (five test pieces were measured and cotton ignited. Number). (10) Rigidity: Flexural modulus was measured according to the test method of JIS K7203. Specimen dimensions (100 × 10 × 4mm),
Bending speed 1.5 mm / min. (11) Moldability (hollow molded product): Evaluate the drawdown property when molding a molded product having a molding temperature of 210 ° C., a uniform parison thickness, a parison length of 700 mm, a weight of 1200 g and a product weight of 580 g (◎). : Molding with almost no drawdown can be performed. ○: Slight drawdown can be seen, but there is no problem as a product. △: Moldable but drawdown occurs and the thickness of the molded product fluctuates. Molding impossible).

The polypropylene resin, the flame retardant, the flame retardant auxiliary and the inorganic filler which are the base resins used in the following Examples and Comparative Examples are abbreviated as follows. [Base resin (A)] A-1 to A-6 polyolefin (co) polymer compositions shown in Table 1 below were used. The production methods are described below.

A-1 (1) Preparation of transition metal compound catalyst component Decane 0. 1 was prepared in a stainless steel reactor equipped with a stirrer.
3 liters, 48 g of anhydrous magnesium chloride, 170 g of n-butyl orthotitanate and 195 g of 2-ethyl-1-hexanol were mixed, and the mixture was heated to 130 ° C. while stirring.
The mixture was heated for a period of time to dissolve to form a uniform solution. This homogeneous solution was heated to 70 ° C., 18 g of di-i-butyl phthalate was added with stirring, and after 1 hour, 520 g of silicon tetrachloride was added over 2.5 hours to precipitate a solid.
For 1 hour. The solid was separated from the solution and washed with hexane to give a solid product.

The total amount of the solid product was mixed with 1.5 liter of titanium tetrachloride dissolved in 1.5 liter of 1,2-dichloroethane, and 36 g of di-i-butyl phthalate was added. After the reaction, the liquid phase was removed by decantation at the same temperature, and 1.5 l of 1,2-dichloroethane and 1.5 l of titanium tetrachloride were added again. 2.8% by weight of titanium
, A titanium-containing supported catalyst component (transition metal compound catalyst component).

(2) Preparation of Pre-Activated Catalyst After replacing a stainless steel reactor having an inner volume of 5 liters with inclined blades with nitrogen gas, 2.8 liters of n-hexane was added.
Triethyl aluminum (organic metal compound (AL1))
9.0 g of 4 mmol and the titanium-containing supported catalyst component prepared in the preceding paragraph (5.26 mmol in terms of titanium atoms)
After the addition, 20 g of propylene was supplied, and prepolymerization was performed at −2 ° C. for 10 minutes. Separately, when the polymer produced by the prepolymerization performed under the same conditions was analyzed, 2 g of propylene became polypropylene (B) per 1 g of the titanium-containing supported catalyst component, and 13 g of polypropylene (B) was obtained.
1. Intrinsic viscosity [η _B ] measured in tetralin at 5 ° C.
It was 7 dl / g. After completion of the reaction time, unreacted propylene is discharged out of the reactor, and the gas phase of the reactor is replaced with nitrogen once. Then, while maintaining the temperature in the reactor at -1 ° C, the pressure in the reactor is reduced. Was maintained at 0.59 MPa, ethylene was continuously supplied to the reactor for 2 hours to perform preactivation. Separately, as a result of analyzing the polymer formed by the preactivation polymerization performed under the same conditions, 32 g of the polymer was present per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity of the polymer measured in tetralin at 135 ° C. [ η _T2 ] was 30.2 dl / g.

The amount (W ₂ ) of polyethylene (A) per 1 g of the titanium-containing supported catalyst component produced by the preactivation polymerization with ethylene is the amount of the polymer produced per 1 g of the titanium-containing supported catalyst component after the preactivation treatment. The difference between (W _T2 ) and the amount of polypropylene (B) produced per gram of the titanium-containing supported catalyst component after prepolymerization (W ₁ ) is determined by the following equation. W ₂ = W _T2 −W ₁

The intrinsic viscosity [η _A ] of the polyethylene (A) produced by the preactivation polymerization with ethylene is the intrinsic viscosity [η _B ] of the polypropylene (B) produced by the prepolymerization and the intrinsic viscosity [η _B ] produced by the preactivation treatment. From the intrinsic viscosity [ηT ₂ ] of the polymer thus obtained, it can be obtained by the following equation. [η _A ] = ([η _T2 ] × W _T2 − [η _B ] × W ₁ ) / (W _T2 −W ₁ )
= [Η _E ]

The amount of polyethylene (A) produced by preactivation polymerization with ethylene according to the above formula is 22 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _A ] is 3
It was 4.0 dl / g. After completion of the reaction time, unreacted ethylene is discharged to the outside of the reactor, and the gas phase of the reactor is replaced with nitrogen once, and then diisopropyldimethoxysilane (electron donor (E1)) 1.6 is introduced into the reactor. After the addition of mmol, 20 g of propylene was supplied, and the mixture was kept at 1 ° C. for 10 minutes to perform addition polymerization after the preactivation treatment.

Separately, the analysis results of the polymer formed by the addition polymerization performed under the same conditions show that the intrinsic viscosity of 26 g of the polymer per 1 g of the titanium-containing supported catalyst component was measured and the polymer was measured in tetralin at 135 ° C. [Η _T3 ] is 29.2 dl / g, and the amount of polypropylene produced by addition polymerization (W ₃ ) calculated as described above
Was 2.2 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _C ] was 2.8 dl / g. After the reaction time, unreacted propylene was discharged outside the reactor, and the gas phase of the reactor was replaced with nitrogen once to obtain a preactivated catalyst slurry for main (co) polymerization.

(3) Production of Polypropylene Composition (Main (Co) polymerization of Propylene) A stainless steel polymerization vessel equipped with a 500-liter internal volume stirrer was purged with nitrogen.
0 liter, 780 mmol of triethylaluminum (organic metal compound (AL2)), 78 mmol of diisopropyldimethoxysilane (electron donor (E2)) and 1/2 of the pre-activated catalyst slurry obtained above were introduced into the polymerization vessel. did. Subsequently, 55 liters of hydrogen were introduced into the polymerization vessel, and the temperature was raised to 70 ° C. Then, propylene was continuously fed while maintaining the gas phase pressure in the polymerization vessel at 0.79 MPa under the condition of a polymerization temperature of 70 ° C. For 2 hours to carry out main polymerization of propylene.

After the elapse of the polymerization time, 1 liter of methanol was introduced into the polymerization vessel, the catalyst was deactivated at 70 ° C. for 15 minutes, and after the unreacted gas was discharged, the solvent was separated and the polymer was dried. Has an intrinsic viscosity [η _T ] of 1.63 dl / g.
40.1 kg of a polymer were obtained. The resulting polymer is
Component (a) is a polypropylene composition having a polyethylene (A) content of 0.25% by weight by preactivated polymerization, and the intrinsic viscosity [η _P ] of the component (b) polypropylene is 1.63 dl / g. there were.

To 100 parts by weight of the obtained polypropylene composition, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 0.1 part by weight of calcium stearate were mixed. It granulated at 230 degreeC using the extrusion granulator of 40 mm in diameter, and was set as the pellet. Various physical properties of the pellets were evaluated and measured.
Was 8.1 g / 10 minutes, the crystallization temperature was 122.7 ° C., and the melt tension (MS) was 2.4 cN. See Table 1 for detailed physical properties
Are shown together.

A-4, A-5 A-1 was prepared under the same conditions as in A-1, except that the amount of polyethylene (A) was changed by changing the conditions of the preactivation polymerization with ethylene. The composition was manufactured, and evaluation samples of A-4 and A-5 were prepared. Table 1 shows the physical properties of the obtained polypropylene composition.

A-3 (1) Preparation of transition metal compound catalyst component Under the same conditions as in A-1, a titanium-containing supported catalyst component was obtained. (2) Preparation of preactivated catalyst A preactivated catalyst slurry was obtained under the same conditions as in A-1. (3) Production of Polypropylene Composition (Main (Co) polymerization of Propylene) In A-1, hydrogen was added so that the hydrogen concentration ratio relative to the propylene concentration in the polymerization reactor (I) was 0.002, and the hydrogen was further added in the polymerization reactor. The propylene was supplied into the polymerization reactor such that the pressure of the solution maintained 1.77 MPa, and the polymerization step (I) was performed.

Separately, the analysis result of the polymer obtained by the polymerization step performed under the same conditions shows that the MFR is 1.1 g / 1.
It was 0 minutes. The intrinsic viscosity [η _T ] of the polymer measured in tetralin at 135 ° C. was 2.39 dl / g.
Intrinsic viscosity [η _P ] of polypropylene in polymerization step (I)
Was 2.32 dl / g. The polymer obtained above is continuously supplied to the polymerization vessel (II) at 60 ° C., and the hydrogen concentration ratio and the ethylene concentration ratio to the propylene concentration in the polymerization vessel are maintained at 0.003 and 0.2. In addition, the polymerization step (II) was performed by supplying the pressure in the polymerization vessel so as to maintain 1.57 MPa. During the polymerization period, the polymer was withdrawn at a rate of 9.4 kg / h from the polymerization vessel so that the level of the polymer held in the polymerization vessel was 60% by volume.

[0094] The extracted polymer was replaced with 5% by volume of steam.
Contact treatment with nitrogen gas at 100 ° C for 30 minutes,
A polymer having an intrinsic viscosity [η _T ] of 2.69 dl / g was obtained. The content of polyethylene (A) produced by the preactivation treatment in the polymer is 0.21% by weight, and the intrinsic viscosity [η _P ] of the propylene / α-olefin block copolymer composition (b) is 2.63 dl / g. Met. The polymerization amount ratio of the polymerization step (I) and the polymerization step (II) is
A copolymer was prepared in which the reaction amount ratio of propylene was changed. Using this as a standard sample, a calibration curve was created using an infrared absorption spectrum, and the ethylene / propylene reaction ratio in the polymerization step (II) was determined. The values calculated from the contents are shown in Table 3.

Subsequently, the mixture was granulated with an extrusion granulator under the same conditions as in A-1 to obtain polymer pellets. This pellet was evaluated and measured for various physical properties.
R was 0.52 g / 10 min, the crystallization temperature was 121.9 ° C., and the melt tension (MS) was 5.2 cN.

A-2 (1) Preparation of transition metal compound catalyst component A titanium-containing supported catalyst component was obtained under the same conditions as in A-1. (2) Preparation of pre-activated catalyst A pre-activated catalyst slurry was obtained under almost the same conditions as in A-1. (3) Production of Polypropylene Composition (Main (Co) polymerization of Propylene) After replacing a stainless steel polymerization vessel equipped with a stirrer with an inner volume of 500 liters with nitrogen, at 20 ° C n-hexane 24
0 liter, 780 mmol of triethylaluminum (organic metal compound (AL2)), 78 mmol of diisopropyldimethoxysilane (electron donor (E2)) and 1/2 of the pre-activated catalyst slurry obtained above were introduced into the polymerization vessel. did. Subsequently, 100 liters of hydrogen was introduced into the polymerization vessel, and the temperature was raised to 70 ° C. Then, propylene was continuously fed while maintaining the gas phase pressure in the polymerization vessel at 0.79 MPa at a polymerization temperature of 70 ° C. For 90 minutes into the polymerization vessel to perform the polymerization step (I). After the completion of the polymerization step (I), the supply of propylene was stopped, the temperature in the reactor was cooled to 30 ° C., and propylene unreacted with hydrogen was discharged. Then, a part of the polymerization slurry was extracted, and the MFR was measured to be 7.5.

After the temperature in the vessel was raised to 60 ° C., 30 liters of hydrogen were introduced into the polymerization vessel, and ethylene and propylene were continuously supplied for 2 hours so that the ethylene supply ratio became 35% by weight. The total supply of ethylene was 7.5 kg. After the polymerization time, 1 liter of methanol was introduced into the polymerization vessel, and a catalyst deactivation reaction was performed at 70 ° C. for 15 minutes.
Subsequently, after discharging the unreacted gas, the solvent was separated and the polymer was dried to obtain 40.5 kg of a polymer having an intrinsic viscosity [η _T ] of 1.95 dl / g.

The obtained polymer had a polyethylene (A) content of 0.2 by preactivated polymerization corresponding to the component (a).
6% by weight of a propylene / α-olefin block copolymer composition, and the intrinsic viscosity [η _P ] of the propylene / α-olefin block copolymer composition (b) of the component (b) is 1.87 dl / g. there were. The polymerization amount ratio of the polymerization step (I) and the polymerization step (II) is determined by preparing a copolymer in which the reaction amount ratio of ethylene / propylene is changed in advance, using this as a standard sample, and preparing a calibration curve in an infrared absorption spectrum. The ethylene / propylene reaction amount ratio in the step (II) was determined, and the value calculated from the ethylene content in the whole polymer is shown in Table 3. Subsequently, the mixture was granulated with an extrusion granulator under the same conditions as in Example 1 to obtain polymer pellets. The pellets were evaluated for various physical properties, and as a result, MFR was measured.
Was 3.0 g / 10 min, the crystallization temperature was 121.5 ° C., and the melt tension (MS) was 2.1 cN.

A-4 After replacing a reactor equipped with a stirrer equipped with inclined blades with nitrogen gas, a catalyst obtained by combining a titanium-containing catalyst component comprising a titanium trichloride composition with diethylaluminum chloride and diethylene glycol dimethyl ether as a third component And the intrinsic viscosity [η _T ] obtained by slurry polymerization of propylene in n-hexane is 1.67 dl.
/ G, 10 kg of propylene homopolymer powder having an average particle size of 150 μm. The operation of evacuating the reactor and supplying nitrogen gas to atmospheric pressure was repeated 10 times, and then di-2-ethylhexyl having a concentration of 70% by weight in toluene solution at 25 ° C. under a nitrogen gas atmosphere with stirring. 0.35 mol of peroxydicarbonate (modifier) was added and mixed. Subsequently, the temperature in the reactor was increased to 120 ° C., and the reaction was performed at the same temperature for 30 minutes. After the elapse of the reaction time, the temperature in the reactor was increased to 135 ° C., and post-treatment was performed at the same temperature for 30 minutes. After the post-treatment, the reactor was cooled to room temperature, and then opened to obtain polypropylene.

To 100 parts by weight of the obtained polypropylene composition, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 0.1 part by weight of calcium stearate were mixed, and the mixture was screwed. A pellet was formed by granulating at 230 ° C. using an extrusion granulator having a diameter of 40 mm.
4 evaluation samples were prepared.

[0101]

[Table 1]

[Flame retardant B] B-1: Bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone. B-2: 2,2-bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane. B-3: 1,2-bis (2 ', 3', 4 ', 5', 6'-pentabromophenyl) ethane. [Flame retardant] Antimony trioxide: specific gravity 5.2, average particle size 2 to 7 μm. [Inorganic filler] Talc: specific surface area 44,000 cm ² / g, average particle size 1.6 μm, component 0.5% by weight having a particle size of 10 μm or more, Mg
33.1% by weight of O component, 62.5% by weight of SiO ₂ component,
Other 0.45% by weight.

The flame-retardant polyolefin compositions shown in Tables 2, 3 and 4 are obtained by blending the above-mentioned base resin, flame retardant, flame retardant auxiliary and inorganic filler with an antioxidant, a neutralizing agent and the like. After homogeneously mixing with a Henschel mixer, the mixture was melt-kneaded with an extruder at 210 ° C., and the strand was cooled and cut to obtain a pellet-shaped composition. The obtained pellet-shaped composition was molded into a predetermined damper, and each of the flexural modulus, self-extinguishing property, cotton ignition property, and moldability (drawdown) was measured. Tables 2 to 5 show the conditions and results.

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

As is clear from Tables 2 to 5, the flame-retardant polyolefin compositions of Examples of the present invention have extremely high melt tension, improved framing drip property during combustion, and can secure an excellent flammability class. Was.

[0109]

As described above, the resin composition of the present invention is obtained by adding polyethylene having a high degree of polymerization together with a catalyst at the time of propylene polymerization to a polypropylene having an improved melt flow rate characteristic and a specific halogen content. By adding a flame retardant and a flame retardant auxiliary, it was possible to provide a flame-retardant resin composition having improved shape retention and flaming drip during combustion without impairing the mechanical properties of flame-retarded polypropylene. .

Claims (5)

[Claims] (1) It comprises an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of an ethylene polymerized unit and has an intrinsic viscosity [ηE] of 15 dl / g measured in tetralin at 135 ° C. 100 dl / g
And (b) 100 parts by weight of a propylene-ethylene block copolymer containing 50% or more of a propylene homopolymer or a propylene polymer unit. The composition has a melt flow rate (hereinafter abbreviated as MFR) [230 ° C .; 21.18 N] of 0.1 to 50 g / 10 min, a melting point (Tm) of 150 to 167 ° C., and a density of 0.895 to
0.910 g / cm ³ , melt tension at 230 ° C is 1 cN
And a flame retardant (B) having a halogen content of 50 to 80% by weight.
A flame-retardant polyolefin composition (C) having an MFR (230 ° C .; 21.18 N) of 0.1 to 50 g / 10 min, comprising from 50 to 50 parts by weight and a flame retardant aid. 2. The periodic table (19) wherein the polypropylene composition (A) according to claim 1 has a molar ratio of 0.01 to 1,000 mol per 1 mol of a transition metal atom containing at least a titanium compound.
1991 edition) 0 to 5 for 1 mol of an organometallic compound [AL1] and a transition metal atom of a metal selected from the group consisting of metals belonging to Groups 1, 2, 12 and 13;
A polyolefin production catalyst comprising a combination of 00 mol of the electron donor [Ed1], and 0.01 to 100 g of 1 per 1 g of the transition metal compound component supported on the catalyst.
When the intrinsic viscosity [η] measured in tetralin at 35 ° C. is 15
dl / g of polypropylene (aP) for the purpose of main (co) polymerization and 0.1 g / g of the transition metal compound catalyst component.
In the presence of a preactivated catalyst consisting of polyethylene (aE) having an intrinsic viscosity [η] of 15 to 100 dl / g measured in 135 g of tetralin at 135 g of 01 g to 5,000 g,
(A) An ethylene homopolymer or an ethylene-olefin copolymer containing 50% or more of ethylene polymer units, which is obtained by (co) polymerizing propylene alone or propylene and an olefin having 2 to 12 carbon atoms. The intrinsic viscosity [η] measured in tetralin is 15 to 100 dl /
g) of polyethylene and 0.01 to 5 parts by weight, and (b) 100 parts by weight of a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units, MFR [230 ° C; 21.18N] of the product is 0.1 to 50 g / 10min,
Melting point (Tm) 150-167 ° C, density 0.895-
0.910 g / cm ³ , melt tension at 230 ° C is 1 cN
And a flame retardant (B) having a halogen content of 50 to 80% by weight.
A flame-retardant polyolefin composition (D) having an MFR (230 ° C .; 21.18 N) of 0.1 to 50 g / 10 min. 3. The flame-retardant polyolefin composition (E) for injection molding, wherein the flame-retardant polyolefin composition (C) or (D) according to claim 1 or 2 has an MFR of 4 to 50 g / 10 min. . 4. A flame-retardant polyolefin composition for hollow or extrusion molding wherein the flame-retardant polyolefin composition (C) or (D) according to claim 1 or 2 has an MFR of 0.1 to 4 g / 10 min. Object (F). 5. The flame-retardant polyolefin composition (C), (D), (E) or (F) according to claim 1.
The flame retardant (B) to be blended is decabromodiphenyl ether, 1,2-bis (2 ', 3', 4 ', 5', 6'-pentabromophenyl) ethane, N, N'ethylene-bis (tetrabromo Phthalimide), perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A, tetrabromobisphenol S, 2,2-bis [[3,5-dibromo- 4- (2´, 3´
-Dibromopropyloxy)] phenyl] propane and bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone, which is at least one halogen-based flame retardant Functional polyolefin composition (G).