JP3510313B2 - Flame-retardant polyolefin-based resin composition with suppressed occurrence of eyes and eyes - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant olefin polymer resin composition. This resin composition is particularly suitable for insulating layers and sheath layers of electric wires and cables, which suppresses the generation of eyes and eyes during extrusion processing, has excellent flame retardancy, and has excellent mechanical properties and can be molded into various molded products. Used for.

[0002]

2. Description of the Related Art Polyolefin resins having excellent electric insulation properties have been widely used as materials for insulating layers and sheath layers of electric wires and cables, but recently, high flame retardancy has been required. For example, the UL standard requires a high degree of flame retardancy of V-1 to V-0. Flame retardant can be made by blending flame retardants such as organic halogen compounds, vinyl chloride polymer, chlorinated polyethylene, etc. with polyolefin resin, but fire dripping occurs, there is a large amount of smoke during combustion, and it is toxic during combustion. There are drawbacks such as generation of various gases and corrosiveness of metals. In order to solve these drawbacks, a method of incorporating a metal hydroxide as a flame retardant into a polyolefin resin has been proposed. Among metal hydroxides, magnesium hydroxide has a decomposition temperature of about 36.
0 ° C, which is sufficiently higher than the processing temperature of polyolefin resin,
Since it does not foam comparatively during molding, it has been used as a flame retardant for flame-retardant polyolefin resin compositions for sheath layers of various communication cables and the like. However, U
In order to satisfy the high flame-retardant standards of V-1 to V-0 of L standard, it is necessary to make the olefin polymer highly filled with magnesium hydroxide in an amount of 60 to 65%. It was not always satisfactory because eyes were generated on the surface of the extruder die during the molding process, and the appearance of the insulating layer of the wire / cable and the sheath layer was impaired due to this. Therefore, although a study of combining an organic flame retardant and an inorganic flame retardant in a polyolefin resin has been studied, the problems in the molding process have not been solved.

[0003]

As described above, a polyolefin resin composition containing an inorganic flame retardant typified by magnesium hydroxide has many excellent characteristics, but it satisfies high flame retardancy standards. In order to reduce the mechanical properties of the molded product, it is necessary to increase the amount of the inorganic flame retardant added. Bring Further, even if a combination of an organic flame retardant and an inorganic flame retardant is blended with a polyolefin resin, the above-mentioned problems in molding processing have not been solved. The problem to be solved by the present invention is to solve the problems of these conventional techniques.

[0004]

The object of the present invention is to provide a flame-retardant resin composition in which ultra-low density polyethylene as a polyolefin resin is blended with a specific amount of acid-modified ethylene polymer and a specific amount of flame retardant is blended. This is solved by incorporating a specific amount of polyolefin-modified polysiloxane into the product. That is, the present invention is as follows. (1) Resin component 100 obtained by mixing 1 to 80 parts by weight, preferably 10 to 50 parts by weight of an acid-modified ethylene-based polymer with 100 parts by weight of ultra-low density polyethylene having a density of 0.87 to 0.91 g / cm ^3. 5 to 250 parts by weight, preferably 20 to 200 parts by weight of a flame retardant is mixed with 100 parts by weight of the resin component and the flame retardant, and a high-pressure low-density polyethylene is used.
Ren, ethylene-vinyl acetate copolymer, ethylene
-Ethyl acrylate copolymer, ethylene-methyl ac
Relate copolymer, ethylene-acrylic acid copolymer,
Tylene-vinyl alcohol copolymer or linear ultra-low density
Degree, low density, medium density or high density ethylene-α-ole
Ethylene-based polymer or polymer selected from fin copolymers
Polyolefins selected from ropylene polymers and vinyl
Rumethyl-dimethylpolysiloxane or vinylmethyl-
0.01 to 100 parts by weight of polyolefin modified polysiloxane with phenylmethyl-dimethylpolysiloxane ,
A flame-retardant polyolefin-based resin composition in which the occurrence of eye bleeding is suppressed, which is preferably blended in an amount of 0.5 to 50 parts by weight. (2) The flame-retardant polyolefin-based resin composition as described in (1), wherein the polyolefin-modified polysiloxane is acid-modified.

The ultra low density polyethylene used in the present invention has a density of 0.87 to 0.91 g / cm ³ and is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. Ethylene accounts for 50 wt% or more, and preferably 70 wt% or more. Examples of the α-olefin include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, 4-methylhexene-1,4,4-dimethyl-pentene-1, octene. −
1, decene-1, dodecene-1, etc. can be illustrated. As a method for producing ultra-low density polyethylene used in the present invention, a catalyst produced by a combination of a transition metal compound of Groups IV to VIII of the periodic table and an organometallic compound of Group I to III, a so-called Ziegler catalyst is used. It is manufactured in the gas phase, and the temperature and pressure conditions can be lower and lower than those of conventional high-pressure polyethylene.

More specifically, the ultra-low density polyethylene used in the present invention has a composition of (a) 0.3 at a temperature of 10 to 80 ° C. in a fluidized bed reaction zone and a pressure of 7,000 KPa or less.
At least one α-olefin having ethylene and 3 to 12 carbon atoms in a molar ratio of 5: 1 to 8: 1 α-olefin to ethylene, and (b) at least 25 mol% of at least one dilution. A gas mixture containing a gas is represented by the formula: Mg _m Ti (OR) _n X _p [ED] _q [wherein R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR '. Wherein R'is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, X is selected from the group consisting of Cl, Br, I and mixtures thereof and ED is aliphatic Or an organic electron-donating compound selected from the group consisting of aromatic alkyl esters, aliphatic ethers, cyclic ethers and aliphatic ketones, m is 0.5 to 56, n is 0, 1 or 2 Yes, p is 2-116 , Q is 2
85. With the catalyst system particles comprising a precursor composition having the formula: and the precursor composition being diluted with an inert carrier material and having the formula: Al (R ') _{d X'e} H _f , X'is Cl or OR ", R'and R" are saturated hydrocarbon groups having 1 to 14 carbon atoms,
e is 0 to 1.5, f is 0 or 1, and d + e
+ F = 3. ] With an organoaluminum compound having a ratio of total aluminum to titanium of 10: 1 to 40 in the reaction zone.
It is produced by a continuous production method characterized in that it is used in an amount of 0: 1.
No. 011 is described in detail.

The acid-modified ethylene-based polymer used in the present invention is obtained by adding an unsaturated carboxylic acid or its derivative to the ethylene-based polymer using a radical generator such as an organic peroxide. The unsaturated carboxylic acid used for the acid modification includes acrylic acid, methacrylic acid, crotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like. As the unsaturated carboxylic acid derivative, maleic anhydride, itaconic anhydride,
Anhydrides such as citraconic anhydride, epoxies such as glycidyl acrylate and glycidyl methacrylate, hydroxy compounds such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, sodium acrylate, sodium methacrylate, acrylic acid Examples thereof include metal salts such as zinc, and these may be used alone or in combination of two or more kinds.

The ethylene polymer is a high-pressure low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer,
Examples include ethylene-vinyl alcohol copolymer, linear ultra-low density, low density, medium density or high density ethylene-α-olefin copolymer, which may be used alone or in combination of two or more kinds. You may mix and use it. The amount of unsaturated carboxylic acid or its derivative contained in the acid-modified ethylene polymer is preferably in the range of 0.005 to 5 mol%. The amount of the acid-modified ethylene polymer blended is preferably 1 to 80 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of ultra-low density polyethylene. If the blending amount is less than 1 part by weight, the mechanical properties and the like of the molded article will deteriorate when the blending amount of the flame retardant is increased, so that the blending amount of the flame retardant cannot be increased and the flame retardancy deteriorates. . On the other hand, if the blending amount is more than 80 parts by weight, eyes and eyes will be generated at the time of molding and mechanical properties of the molded product will be deteriorated, which is not desirable.

The flame retardants used in the present invention include, for example, inorganic flame retardants, halogen flame retardants and phosphorus flame retardants. As the inorganic flame retardant, aluminum hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide,
Calcium phosphate, zirconium oxide, titanium oxide, zinc oxide, magnesium oxide, magnesium carbonate, calcium carbonate, barium sulfate, barium borate, barium metaborate, zinc metaborate, anhydrous alumina, molybdenum disulfide,
Clay, red phosphorus, diatomaceous earth, kaolinite, montmorillonite,
Examples thereof include hydrotalcite, talc, silica, white carbon, celite, asbestos and lithopone.

As the halogen-based flame retardant, decabromodiphenyl oxide, ethylene bispentabromobenzene, tris (2,3-dibromopropyl) isocyanate, 2,2-bis (4-hydroxyethoxy-3,5-).
Examples include dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, hexabromophenyl, hexabromobenzene, pentabromodiphenyl ether, brominated epoxy resin, chlorinated paraffin, and the like. .

As the phosphorus-based flame retardant, tris (chloroethyl) phosphate, tris (monochloropropyl) phosphate, tris (dichloropropyl) phosphate,
Triallyl phosphate, tris (3-hydroxypropyl) phosphine oxide, tris (tribromophenyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, glycidyl-α-methyl-β
-Di (butoxy) phosphinyl propionate, butylhydroxymethylphosphonate, di (butoxy)
Examples thereof include phosphinyl propyl amide, dimethyl methyl phosphonate, ethylene bis tris (2-cyanoethyl) phosphonium bromide, ammonium polyphosphate, amine phosphates such as ethylene diamine phosphate, and amine phosphonates. These inorganic, halogen and phosphorus flame retardants may be used alone or in combination. The blending amount of the flame retardant is 5 to 2 with respect to 100 parts by weight of the resin component.
50 parts by weight is desirable, and more preferably 20 to 200. If the blending amount is 5 parts by weight or less, the flame retardancy is insufficient. Further, if the blending amount is 250 parts by weight or more, the molding processability is deteriorated, and at the same time, the mechanical properties, flexibility, low temperature properties and the like of the molded product are deteriorated, which is not desirable.

The polyolefin-modified polysiloxane used in the present invention is a copolymer having a polyolefin unit and a polysiloxane unit in the molecule. The olefin polymer and the organopolysiloxane are heated and kneaded, and both are grafted. The kneaded product obtained by the above method is typical, and the manufacturing method thereof is described in Japanese Patent Application Nos. 63-42218, 63-107616, 63-207221 and 63-63, which are prior applications by the present applicant. -215972, 6
3-305185, Japanese Patent Application No. 1-154699, 1
No. 154700, No. 2-171142, and the like.

As the olefin-based polymer which is one of the components of the polyolefin-modified polysiloxane, a propylene-based polymer can be mentioned in addition to the above-mentioned examples of the ethylene-based polymer.
As the propylene-based polymer, under a known α-olefin stereoregular catalyst such as a Ziegler-Natta type catalyst,
It is a product obtained by homopolymerizing propylene at a relatively low temperature, so-called medium or low pressure, or by copolymerizing propylene with another α-olefin. Specific examples include propylene homopolymer, ethylene-propylene copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 terpolymer.

The organopolysiloxane which is the other component of the polyolefin-modified polysiloxane is represented by the following formula (A): R ¹ _a R ² _b SiO ₂ ( _{4ab) / 2} (A) (wherein R ¹ Represents an aliphatic unsaturated group such as a vinyl group, an allyl group or a methacryl group, and R ² represents an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group such as a methyl group, an ethyl group or a propyl group. Alkyl groups such as, phenyl groups, aryl groups such as tolyl groups, cyclohexyl groups,
It represents a cycloalkyl group such as a cyclobutyl group or a group in which hydrogen bonded to a carbon atom of these hydrocarbon groups is partially substituted with a halogen atom, a cyano group, a mercapto group or the like, and a and b are under the following conditions: 0 < a <1, 0.5 <b <
It represents a numerical value satisfying 3, 1 <a + b <3. ) Is represented. Specific examples thereof include vinylmethyl-dimethylpolysiloxane and vinylmethyl-phenylmethyl-dimethylpolysiloxane.

The polyolefin-modified polysiloxane used in the present invention may be the acid-modified one. The acid-modified polyolefin-modified polysiloxane is obtained by adding the unsaturated carboxylic acid or its derivative to the polyolefin-modified polysiloxane using a radical generator such as an organic peroxide.

The compounding amount of the polyolefin-modified polysiloxane or its acid-modified product is 10 in total of the resin component and the flame retardant.
0.01 to 100 parts by weight is desirable with respect to 0 parts by weight,
It is more preferably 0.5 to 50 parts by weight. If the blending amount is less than 0.01 parts by weight, the effect of suppressing the occurrence of eye bleeding is lost, and conversely if the blending amount is 100 parts by weight or more, the workability is deteriorated and the mechanical properties of the molded product are deteriorated. Is not desirable.

In the flame-retardant olefin polymer resin composition of the present invention in which the occurrence of eye blemishes is suppressed, various conventional additives and auxiliary materials can be added to the resin composition. Examples of various additives and auxiliary materials include stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, cross-linking agents, lubricants, processability improvers, fillers, colorants, and carbon black.

[0018]

[Effect] The resin composition of the present invention has a density of 0.87 to 0.91 as a polyolefin resin component having good electric insulation.
1 to 80 parts by weight of an acid-modified ethylene-based polymer is added to 100 parts by weight of ultra low density polyethylene (g / cm ³ ), and 5 to 250 parts by weight of a flame retardant is added to 100 parts by weight of this resin component. To 100 parts by weight of the total amount of flame retardant, 0.01% of polyolefin-modified polysiloxane or its acid-modified product is added.
Since it is a flame-retardant polyolefin-based resin composition blended in an amount of up to 100 parts by weight, it suppresses the eye blemishes that occur during molding, which was a conventional drawback, passes high flame-retardant standards, and has mechanical properties. Since it is excellent, it is suitable for use in various molded products, especially in the insulation layer and sheath layer of electric wires and cables.

[0019]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. Example 1 The composition shown in Table 1 was applied to a Banbury mixer at 160 ° C. for 1 hour.
After kneading for 0 minutes, granulation was performed to obtain pellets. Using the produced pellets, a strand die was attached to a Brabender extruder for evaluation of the eyes and an extrusion test was carried out at 230 ° C. for 60 minutes, and the presence or absence of the eyes was visually determined. Also, using the produced pellets, a sheet having a thickness of 2 mm obtained by molding at 150 ° C., 100 kg / cm ² , for 3 minutes with a hot press molding machine was used, and JIS K7 was used.
The flame retardancy test according to 201 and the tensile strength and elongation test according to JIS K6760 were performed. The results are shown in Table 1. Examples 2 to 4 and Comparative Examples 1 to 2 The compositions shown in Table 1 were used in the same manner as in Example 1, and the evaluation results are also shown in Table 1.

[0020]

[Table 1]

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-5-117452 (JP, A) JP-A-62-177046 (JP, A) JP-A-2-145632 (JP, A) JP-A-64- 54044 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. A flame retardant is added to 100 parts by weight of a resin component prepared by mixing 1 to 80 parts by weight of an acid-modified ethylene-based polymer with 100 parts by weight of ultra-low density polyethylene having a density of 0.87 to 0.91 g / cm ^3. 5 to 250 parts by weight is added, and 100 parts by weight of the resin component and the flame retardant are added to the high pressure method low density polyethylene.
Ethylene, vinyl acetate copolymer, ethylene
Ethyl acrylate copolymer, ethylene-methyl acrylate
Rate copolymer, ethylene-acrylic acid copolymer, ethylene
Len-vinyl alcohol copolymer or linear ultra-low density
Degree, low density, medium density or high density ethylene-α-ole
Ethylene-based polymer or polymer selected from fin copolymers
Polyolefins selected from ropylene polymers and vinyl
Rumethyl-dimethylpolysiloxane or vinylmethyl-
A flame-retardant polyolefin-based resin composition in which the occurrence of eye bleeding is suppressed, which comprises blending 0.01 to 100 parts by weight of a polyolefin modified polysiloxane with phenylmethyl-dimethylpolysiloxane . 2. The flame-retardant polyolefin-based resin composition according to claim 1, wherein the polyolefin-modified polysiloxane is acid-modified.