JPS5918743A - Flame-retardant composition - Google Patents

Abstract

PURPOSE:To prepare a composition having high flame-retardance, good low- temperature resistance and excellent weatherability, and suitable for injection molding, by compounding a high-density PE, a chlorinated PE and EVA with an inorganic material having Si-O bond in combination with conventional flame retardant. CONSTITUTION:The objective composition can be obtained by compounding (A) a high-density PE having a density of 0.930-0.980g/cm<3>, a melting point of 112-140 deg.C and M.I. of 0.01-100g/10min and having <=8 1-10C side chains per 1,000C atoms of the main chain, with (B) a chlorinated PE having a chlorine content of 20-50wt%, (C) an EVA having a vinyl acetate content of 1-25wt% and an M.I. of 5.0-30g/10min, (D) a halogen-containing organic compound and/or antimony oxide and (E) an inorganic material having Si-O bond (preferably having SiO2-content of >=50wt%). The ratio of each component is defined as follows: 5-50pts.wt. of the component (D) and 5-15pts.wt. of the component (E) are added to 100pts.wt. of a resin composed of 20-60wt% of the component (A), 10-50wt% of the component (B) and >=10wt% of the component (C).

Description

Detailed Description of the Invention ■Object of the Invention The present invention is directed to high-density polyethylene, zero-chlorinated polyethylene, Ωethylene-vinyl acetate copolymer #S■ halogen-containing compound and /l- or D antimony oxide and [F]
The present invention relates to a flame-retardant composition made of an inorganic substance having a 5i-0 bond, and aims to provide a composition that has excellent weather resistance and is suitable for injection molding.

0 BACKGROUND OF THE INVENTION In recent years, demand for flame retardant compositions has been on the rise, and performance requirements for flame retardant compositions have become more severe. For example, when wiring high-voltage distribution lines to construction sites such as civil engineering and construction, it is conventionally used for construction retaining covers that are used to protect nearby structures, trees, etc. The flame retardance was sufficient at V-2 according to the UL-94 standard. However, recently, highly flame-retardant compositions have been desired due to the frequent occurrence of ignition accidents where they are burned at the above-mentioned close locations and melted and dripped9. Therefore, in conventional flame retardant compositions, a large amount of flame retardant is added due to insufficient flame retardancy. Therefore, sufficient mechanical strength and processability cannot be obtained, and large amounts of expensive flame retardants are used, making them expensive.

ffll1 From the above-mentioned structure of the invention, the present inventors have discovered that it has excellent flame retardancy (UL
As a result of various searches to obtain a composition that is suitable for injection molding and has good weather resistance, (v-o) the density is 0.930 = 0.
980 g/cril tea, melting point 112-140℃
and M, I, Ka 0.01 to 10]j9/10
High-density polyethylene having at most 8 carbon atoms per 1000 carbon atoms in the main chain and at most 10 side chains, 0 Amorphous to crystalline chlorine content of 20 to 500
～50 parts by weight of hydrogenated polyethylene, Ω The content of vinyl acetate is 1 to 25 parts by weight hereditary, Katsu M, 1. is 5.0-3
Ethylene-vinyl acetate copolymer with a 0g710min content: High-density polyethylene, chlorinated polyethylene and ethylene
The content of chlorinated polyethylene in the total with vinyl acetate copolymer is 10 to 500 to 50 parts by weight, the content of high density polyethylene is 20 to 600 to 60 parts by weight, and the content of ethylene-vinyl acetate copolymer The proportion of halogen-containing organic substances and antimony oxide is 5 to 50 parts by weight, and the proportion of inorganic substances is 5 to 15 parts by weight, based on 100 parts by weight of these substances. The inventors have discovered that a flame-retardant composition that is a part of the invention not only has good flame retardancy and cold resistance, but also has excellent weather resistance and is suitable for injection molding, and has thus arrived at the present invention.

(2) 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-O according to UL standards, and is highly 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.

(7) It has excellent weather resistance, so even if exposed outdoors for a long period of time, cracks will hardly occur.

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 wires (2) Detention cover for construction (structures, trees, etc.) (3) Detention cover for communication (4) Cable sheath material (5) Concave fire-resistant wire sheath material for firefighting Invention Detailed explanation of (f) High-density polyethylene The high-density polyethylene used in the present invention is preferably a homopolymer of ethylene or ethylene and α-oleph/cA, and particularly preferably 0.930 to 0.972 g/lr/1. be. The density of this high density polyethylene is 0.930
If it is less than g/cA, the tensile strength of the resulting composition is low. In addition, the melting point of this high density polyethylene is 112 to 1
The temperature is 40°C, preferably 115 to 140°C, and more preferably 117 to 140°C. If high-density polyethylene whose melting point exceeds 112° C. is used, the processability of the resulting composition will be low, and welds will occur at the hinge portion, making it easy to crack. Furthermore, the high-density poly:x-chiv:y(DM, Lid 0.01-1
001/10 minutes, from 0.1 to 50. ! 9/1.0
minutes, particularly 5 to 50 g/10 minutes.

The M of this high density polyethylene is 1. is 0.01g710
If it is less than 1 minute, the moldability of the resulting composition will be poor. On the other hand, 1
If the time exceeds 0.09710 minutes, the moldability of the composition is good, but a good product cannot be obtained due to lack of appropriate rigidity.

This high-density polyethylene essentially consists of one carbon atom in the main chain.
000 at most, 8 carbon atoms have at most 10 side chains (short chain branches). In the high-density polyethylene of the present invention, the term "essentially" consists of the above-mentioned short chain branches, and also includes those having a very small number of carbon atoms in side chains of 11 or more.

The α-olefin used for producing the high-density polyethylene generally has at most 12 carbon atoms (preferably,
Typical examples include propylene, butene-1, bexene-1,4-methylpentene-1, and octene-1. The copolymerization ratio of α-olefin in this copolymer is usually at most 5
It is heavily inherited.

0 Chlorinated polyethylene The chlorinated polyethylene used in the present invention is obtained by chlorinating polyethylene powder or particles in an aqueous suspension, or by chlorinating polyethylene dissolved in an organic solvent ( (preferably those obtained by chlorination in aqueous suspension). In general, it is non-hereditary or crystalline chlorinated polyethylene with a chlorine content of 20 to 50% by weight, particularly chlorine content of 25 to 4%.
Non-hereditary and crystalline chlorinated polyethylene of weight 5 is preferred.

The polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 10 weight hereditary α-olefins (generally having at most 6 carbon atoms). Its density is generally 0.910-0.9
70/cA. Moreover, its molecular weight is 50,000 to 700,000.

The polyethylene used to produce the above-mentioned high-density polyethylene and this chlorinated polyethylene is ethylene alone, ethylene and propylene, and ethylene and the above-mentioned α-olefin.
er) obtained by copolymerization using a catalyst or a 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, those obtained from a so-called carrier-supported solid catalyst component obtained by supporting a red sea bream sium-containing compound, a compound obtained by treating the magnesium-containing compound with an electron-donating organic compound, and an organoaluminum compound. It is. 1. 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 compound. It is obtained from metal compounds.

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.

Ω Ethylene-vinyl acetate copolymer Furthermore, in the ethylene-vinyl acetate copolymer used in the present invention, the vinyl acetate content is hereditary in the range of 1 to 25 weight ratio, and the content of vinyl acetate is hereditary in the range of 2 to 25 weight ratio.9 Reason 5-2
5 The weight section is hereditary. When using an ethylene-vinyl acetate copolymer with a vinyl acetate content of less than one hereditary,
It has poor flexibility and mechanical strength (and tensile strength). On the other hand, if more than 25% by weight of the ethylene-vinyl acetate copolymer 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 and I of this ethylene-vinyl acetate copolymer are 5o to 30 g/10 min, and 7.
0 to 3] j9/10 minutes is preferable, especially 7.0 to
2Fl/lo is suitable. M, 1. 5. O
When using an ethylene-vinyl acetate copolymer with a yield of less than g/10 min, the moldability of the resulting composition is poor. On the other hand, M, ■
When using an ethylene-vinyl acetate copolymer in which the
Not only does it not have adequate rigidity, but its mechanical strength (and tensile strength) decreases. This ethylene-vinyl acetate copolymer is obtained by copolymerizing ethylene and vinyl acetate in the presence of a radical generator (e.g., an organic peroxide, an azo compound) by a solution polymerization method or an emulsion polymerization method. It is something that exists.

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, paraffin chloride, chlorinated bisphenol A, brominated bisphenol S1, chlorinated diphenyl, brominated diphenyl, chlorinated naphthalene, tris(β-chloroethyl)phosphate, and tris(dibromobutyl). ) Phosphate can be mentioned.

(2) 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 oxides are well known as "rubber/plastic compounded chemicals" as mentioned above.

[F] Inorganic substance having 5i-0 bond The SiOρ content of the inorganic substance having Si-0 bond used in the present invention is usually at least 10% by weight, preferably 30% by weight or more, particularly 50% by weight or more. suitable. In addition, the content of lI20 is usually l, 0-20 weight ratio, 1.0-15 weight ratio is hereditary, especially 1.5-20 weight ratio.
The 15th weight section is hereditary. Furthermore, the particle size of the inorganic substance is generally 10 millimicrons to 30 microns,
In particular, 10 mm to 25 microns is preferable,
Particularly suitable are inorganic substances having a particle size of 15 millimicrons to 25 microns.

Typical examples of inorganic substances with 5i-0 bonds include wet white carbon, calcium silicate, colloidal
Synthetic silicate white carbon containing oxides such as silica, some calcium, aluminum, sodium, iron, ultrafine magnesium silicate, aluminum silicate (clay), talc, nepheline feldspar, mica powder, silica powder,
Examples include diatomaceous earth and silica sand. These 5i-0
Regarding inorganic substances with bonds, their manufacturing methods, physical properties and The product name and other information are listed9, making it a well-known product.

0 Blending ratio (mixing ratio) When producing the flame retardant composition of the present invention, the content of chlorinated polyethylene in the total of high density polyethylene, chlorinated polyethylene and ethylene-vinyl acetate copolymer ( The blending ratio) is 10 to 50% by weight, and 15 to 5% by weight.
0% by weight is preferred hereditary, and 15 to 45% by weight is suitable. If the proportion of chlorinated polyethylene in the total amount exceeds 50% by weight, a composition with excellent flame retardancy can be obtained, but a good bottom shape cannot be obtained due to poor moldability and processability. . On the other hand, if it is less than 10% by weight, a composition with good flame retardancy cannot be obtained. Furthermore, the content (blending ratio) of the ethylene-vinyl acetate copolymer is at least 1
0% by weight, preferably 15% by weight or more, particularly 20% by weight or more.
~45% by weight is preferred. If the proportion of the ethylene-vinyl acetate copolymer in the total of these components is less than 10% by weight, a composition with excellent flexibility cannot be obtained. on the other hand,
When the amount exceeds Lls weight %, a composition with excellent flexibility can be obtained, but a composition with excellent mechanical strength (particularly tensile strength) cannot be obtained. In addition, the blending ratio of high density polyethylene is 20 to 600 to 60 parts by weight, 20 to 550 to 55 parts by weight.
There are 9 parts by weight, 25 to 555 to 55 parts by weight. If the proportion of high-density polyethylene in the total amount is less than 20% by weight, a composition with excellent mechanical strength (particularly tensile strength) cannot be obtained. On the other hand, if the weight exceeds 60, cracks are likely to occur in the weld portion of the molded product.

Further, the halogen-containing organic compound and antimony oxide are blended in a total amount of 5 to 50 parts by weight with respect to 100 parts by weight of the high-density polyethylene, ethylene-vinyl acetate copolymer, and chlorinated polyethylene.
-50 parts by weight is desirable, and 10-45 parts by weight is preferred.

The blending ratio of antimony oxide to the amount of halogen element in 100 parts by weight of a halogen-containing organic compound is generally 1
00 to 600 parts by weight, 100 to 400 parts by weight is preferable, especially 150 to 400 parts by weight from the viewpoint of flame retardancy and bleedability.
400 parts by weight is preferred.

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).
5 to 15 parts by weight of an inorganic substance having a 5i-0 bond is blended to 100 parts by weight of the total amount of high-density polyethylene, chlorinated polyethylene and ethylene-vinyl acetate copolymer in order to impart V-O). Therefore, it is desirable to mix 7 to 15 parts by weight per 9 parts.

In producing the composition of the present invention, high density polyethylene, chlorinated polyethylene, ethylene-vinyl acetate copolymer, halogen-containing organic compound, antimony oxide and
The inorganic substances having an i-0 bond may be used alone, or two or more types may be used in combination.

■ Production of compositions and production of molded productsAlthough the composition of the present invention can be obtained by uniformly blending the above-mentioned materials, it is also possible to obtain the composition of the present invention by uniformly blending the above substances. Additives such as fillers, mold release agents, oxygen, ozone and light (ultraviolet) stabilizers, binders, lubricants, and colorants 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 to mix using a mixer such as an open roll, dry blender, Banbury mixer, and kneader commonly used in the art. Bye. 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 in advance with a dry blender, the mixture may be mixed using an open roll. How to mix).

Also, all of the ingredients may be mixed at the same time, or some of the ingredients may be mixed in advance, and then the remaining ingredients may be mixed into the resulting mixture (for example, high-intensity polyethylene, chlorinated After premixing polyethylene, ethylene-vinyl acetate copolymer, halogen-containing organic compound, and antimony oxide, the resulting mixture and 5
method of mixing inorganic substances having i-0 bonds).

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.

11VD Examples and Comparative Examples The present invention will be explained in more detail with reference to Examples below.

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 conducted after leaving it in a gear oven set at a temperature of 90'C for 96 hours.
Measured according to. Furthermore, the heating deformation test is 90±
After leaving it for 1 hour in a thermostatic chamber set at 2℃,
A test was conducted to determine whether deformation occurs due to softening or the like. In addition, in the cold resistance test, the sheet (thickness 2.5 mm) manufactured as described below was left in a -20℃ constant temperature premises for 1 hour, then bent at 180 degrees and tested to see if any cracks occur. did. Furthermore, the heat resistance test is based on JIS K-691.
Section 5.24 of 1, flame resistance was measured by method A. The flame resistance is Underlight Laboratory (UL) 9.
It was measured according to the 4 method.

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

[High-density polyethylene]

As high density polyethylene, the density is 0.955g/c
polyethylene [M, 1.20 g/10 min, hereinafter referred to as 1-I-IDPE (referred to as a river)] and a density of 0.9
61,! ;'/ctA polyethylene CM, 1
．． 7.8g/l, 0 minutes, below r I-i D P E
(1))j] was used.

[Ethylene-vinyl acetate copolymer]

As an ethylene-vinyl acetate copolymer, the density is 0.93
2 g/crA of ethylene-vinyl acetate copolymer [
M, 1.12. ! 9/10 min, vinyl acetate content 15 parts by weight, hereinafter referred to as "EVA (1)"] and a density of 0.928 & /crA ethylene-vinyl acetate copolymer [M, 1.9 g/10 min , vinyl acetate content 1
0 parts by weight or less rEVA(2)J] was used.

[Chlorinated polyethylene]

As chlorinated polyethylene, the density is 0.940. ! 7/
C4 polyethylene (average molecular weight approximately 200,000) was chlorinated by an aqueous suspension method to produce chlorinated polyethylene with a chlorine content of 30.3 parts by weight [density 1.101/c4].

Mooney viscosity (ML, +4 (120°C)) 82.5, non-quality, hereinafter referred to as rcPE(+)J] and density 0,
930 g/cri polyethylene (average molecular weight approx. 1
50,000) was chlorinated by an aqueous suspension method, and the chlorine content was 30,101 parts by weight (density 1, 13).
jj/cTfl, Mooney viscosity (ML, +4 (1
(20°C)) 1070, crystalline, hereinafter referred to as "CPE (2)"] was produced.

[Halogen-containing organic compound and antimony oxide] As a halogen-containing organic compound, the density is 1.669/cr
A chlorinated paraffin (molecular weight: about 1060, chlorine content: about 70% by weight, hereinafter referred to as "Salt Paraffin J") was used. Also, as antimony oxide, the density was 5.25 g/
crIl, antimony trioxide (hereinafter “5b203
”) was used.

[Inorganic substance having a 5i-0 bond] As an inorganic substance having a 5i-0 bond, ultrafine magnesium silicate powder (density 2.75 g/crtl, specific surface area 20rd'/g, particle size 0.32 to 6 microns, S
iO2 content 62.5 parts by weight, MgO content 30.6
]ii%, ■-120 content 4.999 parts by weight or less
MgO-8iO2), aluminum silicate (density 2.61 ji/crl, particle size 2-5 microns.

Sin, content 50.6 parts by weight, Al2O3 content 34.8 parts by weight, -120 content 1.5 parts by weight,
(hereinafter referred to as ruo3.5i02J), Nrika (density 1.
95. j9/CTfl, specific surface area 19.000 cn
i/g, average particle size 16 mm, SiO2 content 86.5 parts by weight, I20 content 13.0 parts by weight, hereinafter referred to as "5IO2") and calcium silicate (density 2.11/cA, Average particle size 40 mm, specific surface area 40 n?/g, SiO2 content 722
Part by weight CaO content 10% by weight, H20 content 1.
5 parts by weight (hereinafter referred to as rcao-8i02J) was used.

Examples 1 to 13, Comparative Examples 1 to 10 The above composition components (high density polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, halogen-containing organic compound, antimony oxide, inorganic substance having a 5i-O bond) The compounding amounts shown in Table 1 (all parts by weight) and 5 parts by weight of tribasic lead sulfate as a stabilizer (however, no addition was made in Comparative Example 1) were added in advance to 100 to 13 parts by weight.
A composition (mixture) was produced by melt-kneading using a kneader in a temperature range of 0°C. Sheets were prepared from each of the obtained mixtures using a mixing roll set at 50°C. Pellets were created using each of the obtained sheet cuts. Each pellet obtained in this way was processed using an extruder (diameter 50 m+n, L/D 26) at a temperature of 130°C for cylinder 1 and a temperature of 14°C for cylinder 2.
Pelletizing was performed under the conditions of 5° C., cylinder 3 temperature of 150° C., die temperature of 150° C., and rotation speed of 30 revolutions/min to create pellets. These pellets were extruded using an injection molding machine (manufactured by 8 Kogyo Co., Ltd., 5 ounces, cooling time 30 seconds) with a nozzle heater at a temperature of 200°C.
, heater 1 temperature 200℃, heater 2 temperature 17
A sheet was created under conditions of 0°C and the temperature of heater 3 at 160°C. The sheets thus obtained were prepared for the following physical property tests, and tensile strength, heat resistance tests, heat deformation tests, and cold resistance tests were conducted. Furthermore, the flame resistance test was conducted using a press machine set at a temperature of 150°C using the pellets produced by an extruder at 100 Kf/ca.
Heat pressing was performed for 5 minutes under pressure (gauge pressure) to prepare a sheet lath with a thickness of 2.5 mm, and a test was conducted. The results obtained are shown in Table 2.

In Comparative Example 2, injection molding was attempted to create 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. It is clear that it is superior,
As mentioned above, it is clear that it has a promising future as a coating material for high-voltage or low-voltage electric covers, Cape Rune materials, and the like.

Patent applicant Sei Kikuchi, patent attorney representing Showa Denko Co., Ltd. - Continued from page 1 ■ Int, C1, 3 identification code Office reference number (C
08L 23/28 23106 6609-4 J2
3/'08) 6609-4J
(Old inventor Kazuyasu Ozaki 431 Kamisuda-cho, Hodogaya-ku, Yokohama City

Claims (1)

[Claims] ■ Density is 0.930 to 0.980 E//cril, melting point is 112 to 140°C, and melt index is 0.01 to 100 g/l. , high density polyethylene having at most 9 and at most 8 carbons per 1000 carbon atoms in the main chain and at most 10 side chains. 0 Chlorinated polyethylene with a chlorine content of 20 to 50% by weight, which is ungradeable or crystalline, 0 A vinyl acetate content of 1 to 25% by weight, and a melt index of 5.0 to 30g710 minutes ethylene-vinyl acetate copolymer, which is made of halogen-containing organic compounds and/or [F] antimony oxide and [F] inorganic substances having 5i-0 bonds, the high-density polyethylene, chlorinated polyethylene and ethylene- The content of chlorinated polyethylene in the total vinyl acetate copolymer is 10 to 50% by weight, and the content of high density polyethylene is 20 to 60% by weight, but the content of ethylene-vinyl acetate copolymer is The proportion of hereditary reeds is at least 10 parts by weight, the total amount of halogen-containing organic substances and antimony oxide is 5 to 50 parts by weight, and the proportion of inorganic substances is 5 to 15 parts by weight, based on 100 parts by weight of these. Flammable composition.