JPS5920341A - Flame-retardant composition - Google Patents

Abstract

PURPOSE:To provide a flame-retardant compsn. having excellent weather resistance and suitable for use in injection molding, consisting of an ethylene/alpha- olefin copolymer, chlorinated PE, EVA, a halogen-contg. org. compd. or antimony oxide and an inorg. material contg. an Si-O bond. CONSTITUTION:A compsn. consists of an ethylene/alpha-olefin copolymer (A) having a density of 0.9-0.93g/cm<3>, a m.p. of 106-130 deg.C, an MI of 0.01-100g/min and 3-35 C1-C10 alkyl side chains per 1,000 carbon atoms of its main chain, non- crystalline or crystalline chlorinated PE(B) having a chlorine content of 20- 50wt%, EVA(C) having a vinyl acetate content of 1-25wt% and an MI of 5-30g/10min, a halogen-contg. org. compd. (D) and/or antimony oxide (E) and an inorg. material (F) having an Si-O bond in such a proportion that component B accounts for 10-50wt%, component A accounts for 30-80wt%, and component C accounts for 10wt%, respectively, of the combined amount of A+B+C, and each amount of components D, E and F is 5-15pts.wt. per 100pts.wt. of the combined amount of A+B+C.

Description

DETAILED DESCRIPTION OF THE INVENTION ■Object of the Invention The present invention relates to (a) a copolymer of ethylene and α-olefin, [phase]
The present invention relates to a flame-retardant composition comprising antimony oxide and an inorganic substance having a [F]8i-0 bond, and aims to provide a composition that has excellent weather resistance and is suitable for injection molding. .

OD Background of the Invention In recent years, demand for flame-retardant compositions has continued to increase, and performance requirements for flame-retardant compositions have become more severe. For example, when wiring high-voltage power distribution lines to construction sites such as civil engineering and construction, it is difficult to use conventionally when used for construction hold-down covers used to protect nearby structures, trees, etc. In terms of flammability, V-2 was sufficient under the UT-94 standard. However, recently they were burned at the said access point and melted and dripped 9
Due to the current situation where fire accidents are occurring frequently, highly flame-retardant compositions are in high demand. Therefore, in conventional flame retardant compositions, a large amount of flame retardant is added due to insufficient flame retardancy. Therefore, it is expensive because it does not have sufficient mechanical strength and processability, and a large amount of expensive flame retardant is used.

[TII] Based on the above structure of the invention, the present inventors have discovered that the invention has excellent flame retardancy (UL
As a result of various searches to obtain a composition that not only has good weather resistance but also is suitable for injection molding, (2) "Density is 0.900-0.940 jjlcr
d, has a melting point of 106-130°C, and has a melt index (measured according to JIS K-6760 at a temperature of 190°C and a load of 2.16 kg, hereinafter 1'-M, 1.J ) is 0.01 to 10
0 g 710 minutes, and the number of side chain alkyl groups having 1 to 10 carbon atoms is 3 to 35 per 1000 main chain carbon atoms.
(hereinafter referred to as "ethylene-based linear copolymer"), ■ Amorphous or crystalline chlorine content of 20 to 500 to 50 parts by weight polyethylene, O vinyl acetate content is 1 to 25
The weight is 5.0 to 30971.
0 minute ethylene-vinyl acetate copolymer, 0 halogen-containing organic compound and/or D antimony oxide, and an inorganic substance having [F] 5i-0 bond, ethylene-based linear copolymer, chlorinated polyethylene The content of chlorinated polyethylene in the total sum with ethylene-vinyl acetate copolymer is 10 to 400 to 40 parts by weight, and the content of ethylene-based linear copolymer is 30 to 800 to 80 parts by weight. The content of the vinyl acetate copolymer is at least 10 parts by weight, and the ratio of acidification of the nitrogen-containing substance and antimony oxide to 100 parts by weight of these is 5 to 50 parts by weight, A flame retardant composition containing 5 to 15 parts by weight of an inorganic substance has not only good flame retardancy and cold resistance, but also excellent weather resistance, and is suitable for injection molding. We have discovered this and arrived at the present invention.

■ Effects of the Invention The composition obtained by the present invention further has the following characteristics (effects).

(1) Excellent mechanical strength (for example, tensile strength and tensile elongation).

(2) Excellent workability.

(3) Heat resistance is also good.

(4) Regarding flame retardancy, it is equivalent to V-0 according to the UL standard, and is extremely flame retardant.

(5) It is cold resistant and has excellent resistance to stress cracks.

(6) Since moldability is good, molded products with complicated shapes can be manufactured.

(Strength) Due to its excellent weather resistance, there is almost no cracking even if it is exposed outdoors for a long time.

(8) Excellent flexibility.

The composition obtained by the present invention has the above-mentioned effects and can be used in a wide variety of fields. Typical uses are shown below.

(1) Clamp cover for high-voltage or low-voltage electric wires (2) Detention cover for building obstructions (structures, trees, etc.) (3) Detention cover for communications (4) Cape Lunce material (5) Fire-resistant electric wire sheath material for firefighting Detailed Description 8 Ethylene-based linear copolymer The ethylene-based linear copolymer used in the present invention is obtained by copolymerizing ethylene and α-olefin. The density of the ethylene-based linear copolymer is 0.9
00~0.940,! i'/crA, 0,9
05 to 0.9409/cttl is preferred, especially 0
．． 905-0.930 g/cl is suitable. The density of this ethylene-based linear copolymer is 0.900 g/cT
If it is less than tI, the resulting composition will not have sufficient rigidity.

On the other hand, if it exceeds 0.94091 crA, the rigidity is high, but the flexibility is insufficient, so it is not suitable. Also, the melting point is 1
06-130°C, preferably 106-125°C,
A temperature of 110 to 125°C is particularly suitable. Melting point is 106
If an ethylene-based linear copolymer with a temperature below ℃ is used,
The resulting composition has insufficient rigidity and heat resistance.On the other hand, if an ethylene-based linear copolymer with a melting point exceeding 130°C is used, the resulting composition has high rigidity. However, both are unsuitable due to lack of flexibility.Furthermore, M and L of the ethylene-based linear polymer are 001
~100. ! 9/10 minutes, 0.1-50g/10
minutes is preferred, particularly 5 to 30.9/10 minutes. M and I of the ethylene-based linear copolymer.

If the amount is less than 0.01 g for 710 minutes, moldability will be poor. on the other hand,
If it exceeds 100 g and 710 minutes, moldability is good, but a good product cannot be obtained due to lack of appropriate rigidity.

The α-olefin used in the production of the ethylene-based linear copolymer is an α-olefin having at most 12 carbon atoms, and typical examples include propylene, butene-1, hexene-1,4-mer F. -Lebentene-1 and octene-
1 is given. The copolymerization ratio of the α-olefin in this copolymer is usually 1.0 to 18% by weight.

What is short chain branching in this ethylene-based linear copolymer?
Refers to a branch that is sufficiently short compared to the main chain, for example, having less than 10 carbon atoms. On the other hand, a long chain branch means a branch having a length sufficiently comparable to that of the main chain, and having, for example, 10 or more carbon atoms.

0 Chlorinated polyethylene The chlorinated polyethylene used in the present invention can be obtained by chlorinating polyethylene powder or particles in an aqueous suspension, or by chlorinating polyethylene dissolved in an organic solvent. (preferably obtained by chlorination in aqueous suspension). Generally, amorphous or crystalline chlorinated polyethylene with a chlorine content of 20 to 50% by weight is used, and amorphous or crystalline chlorinated polyethylene with a chlorine content of 25 to 45% by weight is particularly preferred. The polyethylene of this chlorinated polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 10 parts by weight of α-olefin (generally having at most 6 carbon atoms). Its density is generally 0.910-0.970/c
It is rtl. Moreover, its molecular weight is 50,000 to 700,000.

Polyethylene and ethylene-based linear copolymers used as raw materials for the production of chlorinated polyethylene are ethylene l
In other words, ethylene and propylene are also combined, and ethylene and the above-mentioned α-olefin are combined into the so-called Ziegler (Ziegler)
GLER) catalyst or Phillips catalyst.

Ziegler's catalyst is a transition metal compound (e.g., a halogen-containing compound of titanium) or a support for the transition metal compound (for example, a halogen-containing compound of titanium)
For example, it is obtained from a so-called carrier-supported solid catalyst component obtained by supporting a magnesium-containing compound (a compound obtained by treating the magnesium-containing compound with an electron-donating organic compound) and an organoaluminum compound. . Phillips catalyst is a carrier-supported catalyst obtained by supporting a chromium or molybdenum oxide or a compound of these oxides and zirconium on a carrier (for example, silica, silica-alumina), or a carrier-supported catalyst obtained by supporting the carrier-supported catalyst and an organic metal. It is obtained from a compound.

The above catalysts are merely typical Ziegler catalysts and Phillips catalysts, and other known catalysts may also be used. The method for producing this copolymer is also a well-known method.

Further, the ethylene-vinyl acetate copolymer used in the present invention has a vinyl acetate content of 1 to 25% by weight, preferably 2 to 25% by weight. 5-2
A weight factor of 5 is preferred. When using an ethylene-vinyl acetate copolymer with a vinyl acetate content of less than 1 weight coefficient,
It has poor flexibility and mechanical strength (especially tensile strength). On the other hand, when an ethylene-vinyl acetate copolymer having a weight coefficient exceeding 25 is used, the flexibility is good, but on the other hand, the balance of physical properties is lost and the moldability of the resulting composition is reduced. Moreover, M of this ethylene-vinyl acetate copolymer, 1. is 5.0 to 309710 minutes, and 7
．． 0 to 30 g/10 min is preferable, especially 70 to 2
5 g and 710 minutes is suitable. M, 1. 5. Og
/10 minutes or less, the moldability of the resulting composition is poor. On the other hand, M,1.
When using an ethylene-vinyl acetate copolymer with a strength exceeding 30 g/10 minutes, the composition has excellent moldability, but either lacks adequate rigidity or has poor mechanical strength (particularly tensile strength). descend. This ethylene-vinyl acetate copolymer is produced by combining ethylene and vinyl acetate with a radical generator (e.g., organic peroxide,
It is obtained by copolymerization in the presence of azo compound).

These ethylene-based linear copolymers, chlorinated polyethylene, and ethylene-vinyl acetate copolymers are widely produced industrially and used in a wide variety of fields.

D Halogen-containing organic compound The halogen-containing organic compound used in the present invention is widely known as a flame retardant. Typical examples include tetrachlorophthalic anhydride, chlorinated paraffin, chlorinated bisphenol A, brominated bisphenol S, chlorinated diphenyl, brominated diphenyl, chlorinated naphthalene, )IJ (β-chloroethyl) phosphate, and tris (dibromo). butyl) phosphate is removed.

0 Antimony oxide Furthermore, the antimony oxide used in the present invention is generally used as a flame retardant aid for the halogen-containing organic compound. Representative examples include antimony trioxide and antimony pentoxide.

These halogen-containing organic compounds and antimony oxide are well known from the aforementioned N Handbook, Rubber/Plastic Compounded Chemicals, etc.

[F] An inorganic substance having a 5i-0 bond or an inorganic substance having an 8i-0 bond used in the present invention.
The content of , , is usually at least 10 parts by weight, and 30 parts by weight.
A weight ratio of 50 or more is preferred, and a weight ratio of 50 or more is particularly preferred. In addition, the content of 1-120 is usually 1.0 to 20% by weight, preferably 1.0 to 15% by weight, and especially 1.0 to 20% by weight.
．． A weight ratio of 5 to 15 is preferred. Further, the particle size of the inorganic substance is generally 10 mm to 30 mm, particularly preferably 10 mm to 25 mm, particularly preferably an inorganic substance having a particle size of 15 mm to 25 mm. .

Typical examples of inorganic substances having 5i-0 bonds include wet white carbon, calcium silicate, colloidal silica, some calcium, aluminum, sodium,
Synthetic silicate white carbon containing oxides such as iron, ultrafine magnesium silicate, aluminum silicate (clay), talc, nepheline feldspar, mica powder, silica powder, silica gravel, silica sand, etc. It will be done. Regarding inorganic substances having these 81-〇 bonds, see Rubber Digest Shasen N Handbook, Rubber/Plastic Compounded Chemicals (Rubber Digest, published in 1970), pages 221 to 25.
The manufacturing method, physical properties, product name, etc. are described on page 3 and are well known.

0 Blending ratio (mixing ratio) In producing the flame retardant composition of the present invention, the proportion of chlorination in the total of the polyethylene-based linear copolymer, chlorinated polyethylene, and ethylene-vinyl acetate copolymer is The content (blending ratio) of polyethylene is preferably 10 to 500 to 50 parts by weight and 15 to 50 parts by weight, particularly 15 to 455 to 50 parts by weight.
There are 45 parts by weight.

If the blending ratio of chlorinated polyethylene in the total amount exceeds 50% by weight, a composition with excellent flame retardancy can be obtained, but a good molded product cannot be obtained due to poor moldability and processability. . On the other hand, if the weight ratio is less than 10, a composition with good flame retardancy cannot be obtained. Furthermore, the blending ratio of the ethylene-based linear copolymer is 30 to 800 to 80 parts by weight.
750-75 parts by weight, especially 35-755-75 parts by weight. If the proportion of the ethylene-based linear copolymer in the total amount is less than 30% by weight, a composition having good mechanical properties (particularly tensile strength) cannot be obtained.

On the other hand, when the weight exceeds 80, the flexibility decreases. Further, the proportion of the ethylene-vinyl acetate copolymer in the total amount is at least 10 parts by weight, preferably 15 parts by weight or more, and particularly 15 to 355 to 35 parts by weight.

If the content of the ethylene-vinyl acetate copolymer in the total amount is less than 10% by weight, a composition with excellent flexibility cannot be obtained.

In addition, the blending ratio of the halogen-containing organic compound and antimony oxide is 5 to 50 parts by weight based on 100 parts by weight of the ethylene linear copolymer, chlorinated polyethylene, and ethylene-vinyl acetate copolymer. Yes, preferably 10 to 50 parts by weight, and 10 to 4 parts by weight
5 parts by weight is preferred. The blending ratio of antimony oxide to the amount of halogen element in 100 parts by weight of the halogen-containing organic compound is generally 100 to 600 parts by weight, and 1
The amount is preferably 00 to 400 parts by weight, and particularly preferably 150 to 400 parts by weight from the viewpoint of flame retardancy and bleedability.

The important point of the present invention is that in addition to the usual flame retardant formulation consisting of a usual flame retardant (halogen-containing organic compound and antimony oxide), it has good moldability and high flame retardancy (UL-944).
v-o)'fr: Si-0 based on 100 parts by weight of the total amount of linear ethylene copolymer, chlorinated polyethylene and ethylene-vinyl acetate copolymer
5 to 15 parts by weight of the inorganic substance having bonds is blended, and it is particularly desirable to blend 7 to 15 parts by weight.

In producing the composition of the present invention, an ethylene-based linear copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, an organic compound containing nitrogen, antisene oxide, and an inorganic substance having an 8i-0 bond are used. Each may be used alone, or two or more types may be used in combination.

Although the composition of the present invention can be obtained by homogeneously blending the above-mentioned substances, it is also possible to obtain the composition of the present invention by uniformly blending the above-mentioned materials. Additives such as fillers, mold release agents, oxygen, ozone and light (ultraviolet) stabilizers, binders, lubricants, and color walking agents may be added depending on the intended use of the composition.

In addition, sulfur vulcanizing agents, sulfur-releasing compound-based vulcanizing agents, amine-based vulcanizing agents, organic peroxide-based crosslinking agents, and organic peroxide-based crosslinking coagents commonly used in the rubber industry and resin industry, etc. Additives may be added depending on the intended use of the composition.

When producing the composition of the present invention, the blending (mixing) method is as follows: Mixing may be carried out using a mixer such as an open roll, a dry blender, a Banbury mixer, and a Nigu mixer commonly used in the art. good. Among these mixing methods, in order to obtain a more uniform composition, two or more of these mixing methods may be applied (for example, after mixing with a dry blender, the mixture may be mixed with an oven roll). How to mix).

Furthermore, all the ingredients may be mixed at the same time, but some of the ingredients may be mixed in advance, and then the remaining ingredients may be mixed into the resulting mixture (for example, ethylene-based linear A method in which a copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, halogen-containing organic compound, and antimony oxide are mixed in advance, and then the resulting mixture is mixed with an inorganic substance having a Si-0 bond)
.

The composition of the present invention may be molded into a desired shape using molding machines commonly used in the rubber industry, such as extrusion molding machines, injection molding machines, compression molding machines, and calender molding machines. In addition, a method of manufacturing a molded product by adding chlorinated polyethylene or the above-mentioned composition and vulcanizing (crosslinking) it in the rubber technology field, that is, a method of simultaneously proceeding vulcanization and molding, is applied. It may be formed into a desired shape.

■B Examples and comparative examples The present invention will be explained in more detail below with reference to Examples.

In addition, in the examples and comparative examples, the tensile test was conducted according to JIS
Measured according to C-3005.

In addition, the heat resistance test was performed in accordance with JISC-3005 after leaving the product in a gear open state at a temperature of 90° C. for 96 hours. Furthermore, the heating deformation is 90±2℃
After being left in a thermostatic chamber set at Also,
The cold resistance test was conducted using sheets manufactured as described below (thickness
2.5 Theory) was left in a -20℃ constant temperature premises for 1 hour,
It was bent at 180 degrees and tested to see if cracks were formed. Furthermore, the heat resistance test was measured according to section 5.24 of JIS K-6911, and the flame resistance was measured according to method A. In addition, the flame resistance is Underwriters Laborad +) - (U L
) Measured according to the 94 method.

The ingredients used in the Examples and Comparative Examples were manufactured by the following shapes, physical properties, and manufacturing methods.

[Ethylene-based linear copolymer]

As an ethylene-based linear copolymer, the density is 0.920.
Linear copolymer of ethylene and butene-1 with g/crA [M, 1.15 g, /lo min, melting point 120°C, number of side chain alkyl groups per 1000 main chain carbon atoms 7, side Alkyl group in the chain Mainly ethyl group, hereinafter referred to as “PE (
A linear copolymer of ethylene and hexene-1 with a density of 0.916 g/ca [M, 1
．． 23. ! i! /10 minutes, melting point: 116° C., number of side chain alkyl groups: 12 per 1000 main chain carbon atoms, butyl group as the main chain alkyl group, hereinafter referred to as rPE (hereinafter referred to as BIJ) was used.

[Chlorinated polyethylene]

As chlorinated polyethylene, the density is 09409/cr
Polyethylene A (average molecular weight approximately 200,000) was chlorinated by an aqueous suspension method to produce chlorinated polyethylene with a chlorine content of 303% by weight [density 1.06.9/cA, Mooney viscosity (y L ++ 4 (120°C)) )82.5, non-quality, hereinafter referred to as 1-CPE(t)] and density is 0,
9319/cA polyethylene (average molecular weight approximately 15
10,000) was chlorinated by the aqueous suspension method, and the chlorine content was 30%.
．． 1% by weight chlorinated polyethylene [density 1.05 g/
crd, Mooney viscosity (M, L, +, (120°C)) 1
07.0, crystalline, hereinafter referred to as rcPE (21J) was manufactured and used.

[Ethylene-vinyl acetate copolymer]

As an ethylene-vinyl acetate copolymer, the density is 0.93
29/crtl ethylene-vinyl acetate copolymer (M, 1.12 g/10 min, vinyl acetate content 15% by weight, hereinafter referred to as rEVA(1)J): I Oyo U density is 0.928 Ethylene-g/crA
A vinyl acetate copolymer [M, 1.9 g/10 min, vinyl acetate content 10% by weight rEV (referred to as 21) was used.

[Halogen-containing organic compound and antimony oxide] As a halogen-containing organic compound, the density is 1.669/c
Chlorinated paraffin (molecular weight: about 1060°, chlorine content: about 70% by weight, hereinafter referred to as "salt paraffin"), which is rA, was used. Also, as antimony oxide, the density is 5.259
/ crIl, antimony trioxide (hereinafter referred to as “5b20
3) was used.

[Inorganic substance with 5i-0 bond] As an inorganic substance with 5i-0 bond, ultrafine magnesium silicate powder (density 2.75 g/crd, specific surface area 2 On?/g, particle size 0.32 to 6 microns) is used. , S
iO□ content 62.5% by weight, MgO content 30.
6% by weight, Fe2O3 content 1.0% by weight, H20 content 4.999% by weight or less rMgO-5in2J), aluminum silicate (density 2.61, !i'
/cl, particle size 2-5 microns, 5I02 content 50.
6 parts by weight, M2O3 content 34.8 parts by weight, I]20
Content: 155 parts by weight or less rA1203.5IO2), silica (density: 1.95 glcrtlv specific surface area: 19,000 cJ/11 Average particle size: 16 millimicrons bs; O2 content: 1865 weight ratio, lI20 content: 13.0 weight (hereinafter referred to as "5I02") and carunium silicate (density 2.1, !li'/c
a, average particle size 40 mm, specific surface area 40 n
l/ji, 5in2 content 722 parts by weight CaO content 100 parts by weight I] 20 content 1.5 parts by weight, hereinafter referred to as "CaO-8IO2").

Examples 1 to I3, Comparative Examples 1 to 9 The above composition components (ethylene-based linear copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, halogen-containing organic compound, antimony oxide, 5i-0 bond) 120 parts by weight of tribasic lead sulfate (not added in Comparative Example 1) and 5 parts by weight of tribasic lead sulfate as a stabilizer.
A composition (mixture) was produced using a kneader in a temperature range of ~140°C with melt mixing. Sheets were prepared from each of the obtained mixtures using a mixing roll set at 50°C. Pellets were created from each of the obtained sheets using sheet cutting.

Using an extruder (diameter 50 mm, L/D 26), the temperature of cylinder 1 was 1.
30℃, cylinder 2 temperature 145℃, cylinder 3
Pelletization was performed at a temperature of 150° C., a die temperature of 150° C., and a rotation speed of 30 revolutions/min to create pellets. These pellets were molded using an extruder using an injection molding machine (manufactured by Niroku 1, 5 ounces, cooling time 30 seconds) with nozzle heater 1 temperature 200°C, heater 1 temperature 200°C, heater 2 temperature 170°C, and The sheet was created under the condition that the temperature of the heater 3 was 160°C. The sheets obtained in this way were prepared for the following physical property tests,
Tensile strength, heat resistance tests, heat deformation tests and cold resistance tests were conducted. Furthermore, the flame resistance test was carried out using a press machine set at a temperature of 150°C using the pellets manufactured using an extruder, and hot-pressed for 5 minutes under a pressure of 100 kg/ca (gauge pressure). A .5 tone sheet was created and tested. The results obtained are shown in Table 2.

In Comparative Example 2, injection molding was attempted to produce a sheet, but the sheet could not be manufactured.

From the results of the above Examples and Comparative Examples, it is clear that the flame-retardant composition obtained by the present invention shows good values in the tensile test, heat resistance test, and cold resistance test, and also has good flame-retardant properties. Since it is clear that the material has excellent properties, it is clear that it has a promising future as a material for high-voltage or low-voltage electric covers, Cape Rune materials, etc. as mentioned above.

Patent applicant: Showa Denko Co., Ltd. Agent: Patent attorney Sei Kikuchi

Claims (1)

[Claims] ■ The density is 0.900 to 0.930 g/cttl, the melting point is 106 to 130°C, the melt index is 0.01 to 100 g710 min, and the number of carbon atoms is substantially is a copolymer of alethylene and α-olefin with 1 to 10 side chain alkyl groups per 1000 main chain carbon atoms, 0, amorphous to crystalline chlorine content of 20 ~500-50 weight parts polyethylene,
0 Ethylene-vinyl acetate copolymer with a vinyl acetate content of 1 to 25% by weight and a melt index of 5.0 to 309710 minutes, ■ halogen-containing organic compound and/or antimony oxide and [F ] The content of chlorinated polyethylene in the total of the inorganic material having Si-0 bonds, the copolymer of ethylene and α-olefin, the chlorinated polyethylene, and the ethylene-vinyl acetate copolymer is 10 to 500. ~5
The content of the copolymer of ethylene and α-olefin is 30 to 800 to 80 parts by weight, the content of the ethylene-vinyl acetate copolymer is at least 10 parts by weight, and the total amount of these is 100 parts by weight. The blending ratio of halogen-containing substances and antimony oxide is 5 as their total amount.
~50 parts by weight, and the blending ratio of the inorganic substance is 5 to 1
5 parts by weight of a flame retardant composition.