JPS58194938A - Flame retardant crosslinked polyethylene insulator - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides crosslinkable polymeric body compositions which are moisture, heat and flame resistant and are useful in the manufacture of molded products as well as insulated wire and cables. More particularly, one of the most overlapping fields of application for 0effi polymer compositions relating to ethylene-vinyl acetate copolymers, which have a high degree of flame resistance.
This is an electrical field where both insulation and integrity are required, and most particularly in the field of insulation of conducting wires. In the past, chlorinated polymers such as chlorinated polyethylene, polyvinyl reinforced, chlorobutadiene, chlorinated paraffin, etc. were used as extrudable compositions available in the wire and cable technology industry for flame resistance purposes. There was a need for a book that contained both antimony and antimony trioxide, and in which both were present in considerable amounts. An alternative method has been to apply a chlorosulfonated polyethylene paint to an insulating composite that is not flame resistant, but this requires additional handling.

Certain types of dry type transformers, particularly high voltage transformers, have had problems with electrical failure due to surface cleaving of the organic insulation composites used. This problem is caused by butyl rubber,
The problem was solved by adding hydrated alumina to a composition using epoxy resin or polyester resin as a binder.However, these compositions have excellent press molding properties, physical and electrical properties, It seems that it has a harmonious combination of heat resistance and flame resistance. The composition is Keracel etc. (K
・U.S. Patent No. 2,99 for 5eal at al)
No. 7,526; No. λ? No. 97.527 and No. 2,99
No. 7,528. The compositions described have poor tensile strength, elongation and percent elongation properties over time for such applications.

The flame-retardant polymer composition, which exhibits particularly improved moisture and heat resistance, comprises as main components one or more crosslinkable polymers, including an ethylene-vinyl acetate copolymer, one or more silanes, and one or more silanes. Essentially intimate incorporation of one or more hydrated inorganic fillers has gained wide acceptance in the wire and cable industry. Such compositions are disclosed in North et al. (US Pat. No. 5,852.526 and No. 4? 22,442
Disclosed in the issue. These percentages are 100 liters by weight of polymer.
80 to 400, preferably 125-1 for the li part
40 parts by weight of filler and 15 to 5.0 parts of silane per 100 parts of filler are disclosed. Although the specific addition range of lubricant is not claimed, 2 parts of calcium stearate to 100 parts of polymer is used in all 14 compositions of the example.

The prior art polymer compositions of North et al. combine improved physical and electrical properties in harmony with a high degree of flame resistance and flame retardancy. Since it does not use halogenated polymers such as vinyl chloride and chlorosulfonated polyethylene, it does not generate hydrogen chloride fumes, and since it does not contain carbon black, it can be used as a colored insulator. Currently, there are 1 degrees, so when using this composition, for example to extrude an insulating composite onto a conductor, it is difficult to perform a manufacturing operation. These highly desirable results are obtained without the additional step of coating with white (in nature) and colored monomers.
Particular applications are concerned as P edge compositions, which can be extruded onto various metals, e.g. copper or aluminium, into single layer insulation and jacket compositions, which meet the U, L test method's operation at 90°C and Operation at temperatures as high as 125° C. in some cases has been shown to be sufficient for voltages up to 600 volts.

North et al.'s insulating compositions uniquely combine excellent electrical properties with inherent resistance to heat and flame degradation, and the advantage of low smoke and non-corrosive smoke. , 1 T-wires, electrical appliances, uos*otasoe*gmg°1 are finding uses.

North et al. contemplate crosslinking the ethylene-vinyl acetate copolymers in their compositions either by radiation from a high energy source or by the use of chemical crosslinking agents.

As has been observed with other radiation-cured polymer compositions, the radiation-cured compositions made according to the disclosure of North et al. have inferior physical strength to their oxide-cured counterparts. 8 Although the cause of this phenomenon is not completely understood, it is believed that the very nature and amount of the main and secondary components of the ripening composition are contributing factors. Attempts have been made to make certain modifications to oxide curable products to make them radiation curable. There, radiation IVjl@! The copolymer in the available product had a high vinyl acetate content and the calcium stearate lubricant was replaced by aluminum stearate. Although this improves the physical strength of radiation-cured compositions over previously existing values, it is still significantly lower than trench-cured peroxide-cured products.

U.S. Patent No. 4.549.6 issued September 14, 1982
No. 05 describes radiation-crosslinked polymer compositions that have substantially improved physical strength properties than their chemically crosslinked counterparts. Using increased amounts of silane and aluminum stearate lubricant
This improved physical strength property was obtained by changing to i Possible additives include #'iS additives, antioxidants, and stabilizers. Antioxidants are added to prevent deterioration of the polymer due to oxidation that proceeds through a chain reaction mechanism of free radicals. Antioxidants can be used to generate the next free radical by bonding with the -(-oxy group, making it impossible for the free radical to propagate the reaction chain, or by decomposing the hydroperoxide into a carbonyl group. The former are called chain-cutting antioxidants, free radical scavengers, or inhibitors, and include sterically hindered hindered phenols and amines.

Agents are called peroxide decomposers and are commonly used to remove yellow compounds (i.e., sulfides, disulfides, sulfoxides, sulfones, thiodipropionic acid esters, etc.) or dithiocarbamates and dithiophosphates. It is a metal complex. U.S. Pat. No. 4.279.8 describes alkylene bis-thioalkanoic acid amides as stabilizers.
Those skilled in the art have also received disclosure of stabilizers for synthetic resins, such as No. 05, for example, as disclosed in the US patent Hashindo et al.
Corrosion inhibitors are also known, such as those described in U.S. Pat. No. 4,124,549 by et al.

・till' Other patent disclosures, Keogh U.S. Patent No. 4
．． 25.5゜□)□・・”□・・No. 305 has electrical resistance, tensile strength and elongation ability, and has ethylene-vinyl acetate, halogenated flame retardant, antimony trioxide, peroxide and stearin. 1 shows compositions for electrical applications consisting of zinc oxides.
U.S. Patent No. a', osss2s of
Antimony tritide and hexapromocyclododecane (H
BCD), chlorinated paraffins, tetrabromo-phthalic anhydride (TBPA), and tetrabromo-terephthalic acid (
Addition of certain organometallic compounds having the chemical structure of substituted hydrazine or 3-amino-1,2,t-)riazolamide to the effect of flame-retardant compositions with various nitrogen-containing compounds (TBTA) However, compositions that have been intentionally increased are described. - The present invention provides a polymeric composition comprising a lubricant system that has lubricant properties and significantly increases the flame resistance of the composition.

It is possible. According to the invention, a silane-treated, nonahydrated, non-containing ethylene copolymer (in particular an ethylene-vinyl acetate copolymer) composition containing a fatty acid having from 8 to 25 carbon atoms. and an alkylene-bis-amide in which the alkylene group has 2 to 8 carbon atoms and the amide component has 8 to 25 carbon atoms. What can be achieved has now been invented. Such a lubricant composition is preferably used in combination with antimony trioxide and a halogenated flame resistant additive to conventional flame resistant hydrated alumina. More particularly, the compositions of the present invention include the use of such lubricants in place of the conventional calcium stearate lubricants normally used in the compositions. The present invention relates to a crosslinkable polymer composition having the following composition:

Copolymer of ethylene and C, -C, vinyl ester of aliphatic carboxylic acid, Cl-C-alkyl ester of acrylic acid or Cl-C-alkyl ester of methacrylic acid, b) 100 parts of copolymer 80 to 400 parts of hydrated inorganic filler, C) 114 to 8, preferably (18 to 4 parts of alkoxysilane, and d) per 100 parts of hydrated inorganic filler;
In addition to the usual flame-resistant hydrated inorganic fillers, halogenated flame-retardants, antimony trioxide, and, quite surprisingly, fatty acids and alkylene-bishairamides having from 8 to 25 tII carbon atoms, provided that the alkylene group It has 2 to 8 carbon atoms, and the amiF group has 8 to 25
The present invention also provides a flame-retardant component comprising a binary lubricant system consisting of: a) ethylene and Cm-cs aliphatic carboxylic acid ester;
Copolymer with Cl-C@alkyl ester of acrylic acid or C,-C alkyl ester of methacrylic acid, and b) Silanized hydrated inorganic filler, a copolymer with a skeleton filler concentration of 100 Department size ranges from 80 to 400 copies.
C) Contains halogenated flame retardant and antimony trioxide
In the composition of the crosslinkable polymer of type 7,
From fatty acids of 25 to 25 carbon atoms and alkylene-bis-amides, where the alkylene group has 2 to 8 carbon atoms and the amide group #'i has 8 to 25 carbon atoms. The present invention also relates to improvements in the use of binary lubricant systems comprising these crosslinkable polymer compositions as flame retardants with extraordinary effectiveness. Concerning an electrical conductor coated with one insulating layer.

The present invention relates to antimony trioxide and I.

The binary lubricant system 21 described above is combined with a non-halogenated flame retardant. Yo1. -2, Ya□A1. .

The present invention relates to a crosslinkable polymeric composition comprising a copolymer of ethylene and aliphatic carboxylic acid vinyl ester, acrylic acid alkyl ester or methacrylalkyl ester and a silanized hydrated inorganic filler. These compositions have particular use in wire and cable insulation.

In addition to the specific lubricant combination, the compositions of the present invention also include:
- a glaze or more halogenated flame retardants and optionally antimony trioxide; - m or more crosslinkable or curable ethylene copolymers; - silane or more silanes and one or more Contains hydrated inorganic fillers.

Copolymers, silanes and inorganic fillers include those disclosed in North Township U.S. Pat. put. 1. 1.:1:■ □1゜The terms "printable" or "crosslinked" are used herein with the meanings recognized by those of ordinary skill in the art, i.e., these terms refer to Let us show that a valence bond is formed. Chemical methods including peroxide crosslinking; crosslinking can be achieved by any known method such as cobalt-60, application of radiation using accelerators, beta-rays, gamma-rays, electrons, X-rays, etc., or thermal crosslinking. It is. The basic techniques of polymer crosslinking are very well known to those skilled in the art and need not be described in detail here. The polymer component of the present invention is a copolymer of ethylene and a comonomer that is either a vinyl ester, an acrylic ester, or a methacrylic ester. Vinyl esters can be vinyl esters of C,-C aliphatic carboxylic acids such as vinyl acetate, vinyl butyropionate, vinyl butyrate, vinyl pentane or vinyl hexanoate.Acrylic acid and methacrylic esters are e.g. Methyl, ethyl, propyl acrylic acid or methacrylic acid,
Cm- containing butyl, pentyl or hexyl-esters
It may be any of C@alkyl ester. Preferred copolymers of the polymeric components of this invention include about 6 to about 90%, preferably about 9 to about 40%, most preferably about 9 to about 28% vinyl acetate and the balance ethylene. The compositions of the invention contain small amounts of other polymers or copolymers that can be crosslinked, although the resulting properties are less beneficial and may even impair the properties of the ethylene-vinyl acetate copolymer. It is possible. However, the ethylene copolymer, fOft, must be about 66 or more of the total amount of the ethylene-vinyl acetate copolymer present.

Alternative examples of small amounts of polymer components that can be used in such undesirable embodiments include polyethylene, copolymers of ethylene with propylene, butenes, acrylic esters and maleic esters, polydimethylsiloxane and polymethylphenyl. Examples include siloxane and copolymers of vinyl acetate and acrylic ester. Of course, mixtures of these minor polymer components can also be used.

Ethylene and vinyl acetate terpolymers derived from monomeric materials (other than ethylene and vinyl acetate), for example corresponding to those listed above, can also be used. A typical terpolymer would be ethylene-vinyl acetate-vinyl maleate terpolymer.

The ethylene-vinyl acetate copolymers used in the present invention preferably have a melt index of about 1.0 to about 2α0.

The polyethylenes useful in this invention are essentially all high, medium and low density polyethylenes and mixtures thereof. The most preferred polyethylenes for blending for use as single insulation in electrical wires and cables generally range from about α900 to about α950.
f7, o1□0ゎ1. . uz! ``'j,..., i, i, ah, yu.

Evidently, the compositions of the present invention retain to an unexpected degree other desirable properties for the use of binary lubricant components: 1) cold brittleness, i.e., the compositions exhibit low temperature kinetics ( ASTMD7
46) Will not be easily destroyed during construction.

2) Heat resistance of the ridge over time, ie excellent elongation after tensile tests up to 90°C and even 125°C.

3) Even porcelain shows surface destruction at 4KV, but at 5KV
resistance to arcing and tracking at high voltages at i, properties that are not often required. This is a preferable environment for use under 6oov. ,.

1. It has better moisture resistance, ie, less permanent mechanical sorption, and has an excellent dielectric constant.

5) Resistance to industrial chemicals.

6.) Resistance to petroleum, gasoline and diesel fuel It is not known why the compositions of the present invention have such excellent and well-balanced properties. Although it is possible that some harmonic relationship exists between the ethylene-vinyl acetate copolymer, the silane, and the hydrated inorganic filler, no attempt is made to theorize this here. However, 5o
For low fr1 pressure environments that are lower than oov, especially 6
It has been established that for environments below 00 volts, the compositions of the present invention are particularly effective for use as single insulators.

Single insulation is a term associated with those skilled in the art in which a single layer is extruded around a conductor, and this single layer acts as an electrical insulator and a jacket for physical and flame protection. It is an insulator that has

The compositions of the invention are particularly suitable for single insulation roles in the sub-500V range, and most particularly in the sub-600V range, where extruded insulation boards are used and which have excellent properties. It is in this environment that harmony is required. It has been discovered that ethylene-vinyl acetate copolymers contain extremely large amounts of filler and yet have both high flexibility and a high degree of crosslinkability. It is generally believed that high flexibility and high crosslinkability go hand in hand.
High crosslinking and high filler loading (which means a lower content of crosslinkable polymers) are also believed to be the case, whereas high filler loading, flexibility The simultaneous achievement of crosslinking and crosslinking properties is quite surprising.

The ethylene-vinyl acetate copolymer also provides excellent flame retardant properties to the polymer compositions of the present invention.

The ethylene-vinyl acetate copolymers described above can be crosslinked by irradiation with a high energy electron beam or by the use of chemical crosslinking agents. Once fully crosslinked, these polymers become thermosetting in nature. In preferred compositions of the invention, chemical crosslinking is preferred, especially where good physical strength is required.

Chemical crosslinking involves adding a crosslinking agent, such as dicumyl peroxide or a,a'bis(
This is accomplished by including t-butylperoxydiisopropylbenzene. The peroxide is later activated during the process and binds the ethylene-vinyl acetate copolymer chains into a three-dimensional network (or other small amounts of cross-linkable polymers, if present). Incorporate it <)
.

Chemical crosslinking is carried out by methods well known in the art, with modifications to the general crosslinking conditions attempted below.26. A6. . 11.1. i='Wl, -C*-
The use of organic peroxides is not limited, and others of the art have recognized that fractionated free radical generating materials can be used. Obviously, such crosslinking agents do not decompose while forming the composition;
However, the selection of crosslinking agents that can be used will be easy for those skilled in the art.

Generally speaking, the degree of crosslinking of the polymer increases as the amount of crosslinking agent used increases. Generally no more than 10% (based on the polymer) of organic tertiary peroxide should be used, with 5 to 6% being typical. Other types of crosslinkers have different requirements! There may be some quantity, but its value can be easily determined. It is often said that the use of very small amounts of crosslinking agent should be avoided, since loss of deformation resistance under sudden or continuous pressure may occur. Crosslinking aids such as triallyl cyanurate and the like may also be added to increase the effectiveness of the crosslinker. ,'l(X Tertiary organic peroxides, like most chemical crosslinkers, are activated by heating above the activation temperature at which their decomposition begins. Methods can be used, such as applying high pressure steam to the composition.

The technology of radiation crosslinking is extremely highly developed, so there is little to add here regarding this method. As the dose of radiation increases, the degree of crosslinking generally increases.

A total radiation dose of about 5-25 megarads may be used for the preferred degree of crosslinking.

Crosslinking is generally carried out at higher than normal pressures, e.g. 200 to 400p.
It is carried out under pressure on the order of s+, is this expensive?
Although lower pressures can also be used. Pressure is required when curing with steam to obtain the temperature necessary to activate the peroxide catalyst. Pressure is necessary to avoid porosity and galling of the insulation. Porosity is highly undesirable in electrical insulation because it reduces electrical insulation properties and can lead to premature failure from corona.

Generally, the higher the degree of crosslinking, the more resistant the polymer composition is to heat, drift, chemical reagents, changes due to aging and environmental conditions, and generally also to abrasion. A low degree of crosslinking results in a slight loss of heat resistance with a significant effect on percent elongation after aging.

Of course, the exact degree of crosslinking can be varied taking into account the factors mentioned above and their influence on the final product. Higher or lower values can be used, but for wire and cable insulation, approximately 85 A value on the order of -95% is generally preferred.

One or more substituent silanes are the second essential component of the polymer compositions of this invention.

Any silane, such as alkoxy and amine silanes, may be used with the proviso that the silane does not create a flammable composition and does not interfere with polymer crosslinking or self-decompose during polymer processing. It is used in the present invention to aid in the association of the polymers of the present invention with the fIE filler without adversely affecting the property match. Preferred silanes for use in the form of insulating compositions include, for example, lower alkyl-
, alkenyl-, alkynyl-, and arylalkoxysilanes, and lower alkyl-, alkenyl-, alkynyl-1, and aryl-alkoxyalkoxy- or aryloxyalkylsilanes. Specific examples of such silanes are methyltriethoxy) methyltris(2-methoxyethoxy)-, dimethyldi-ethoxy-1\a, ya/u-MJ, j) ya, -9=yb) I72
(2-□ Guy°, Pa・・shi,.

These are phenyltris(2-methoxyethoxy)-, vinyltrimethoxy- and vinyltriethoxysilane.

Preferably use vinyl silanes for best quality
Among the vinylsilanes, the following are particularly preferred: and vinyl-tris(2-methoxyethoxysilane Hz
C=CHS i (OCH2CHri0CH3),.

Fillers used in the present invention include, for example, hydrated aluminum oxide (AI 03.3H20 or AI (OH),
), hydrated magnesia, hydrated inorganic fillers such as hydrated calcium silicate, etc. Most preferred is hydrated fC allinium oxide.

11r.

In order to achieve the above-mentioned excellent Moo balance, it is necessary to use hydrated inorganic fillers in the formulation of the polymer composition. Other types of fillers, whether inert or not, may not be able to add to the composition in large enough quantities to become a major part, but have been found to be able to achieve a good balance of properties. We have to fight it hard.

The water in the inorganic filler is heated while applying sufficient heat to cause calcination or ignition of the ethylene-vinyl acetate copolymer.
It must be released. Water chemically bound to the inorganic filler is released endothermically. Hydrated inorganic fillers are superior to other fillers traditionally used in the industry to impart flame resistance to insulation materials, such as carbon black, clay, and titanium dioxide. It was discovered that it increases sex. Even more surprising is that when high filler loadings are used, even though at those loadings the copolymer compositions contain large amounts of bound water,
It combines excellent flame resistance with excellent electrical insulation properties.

The size of the filler may be similar to that of fillers used in the prior art.

Antimonitor compounds that can be included as a component of the polymer compositions of the present invention include diesters of thiodipropionic acid, with the preferred diester being distearyl-3.
, 3'-thiodipropionic acid) (DSTDP). It has been discovered that the use of two different types of antioxidants provides efficient acid protection. Therefore, a mixture of a chain-breaking type antioxidant and a peroxide decomposer type antioxidant results in a highly effective antioxidant composition. Therefore, amines or hindered phenols, which are known peroxide decomposers, can be effectively employed together with DSTDP as an antioxidant composition. Among these free radical scavengers, sterically hindered phenols are particularly effective. Useful phenols include alkylated phenols, alkylidene-bis-alkylated phenols and polyphenols, particular examples of which are 2,6-di-tert-butyl-para-cresol,
5-di-t-butyl-4-hydroxy to octadecyl
Hydrocinamate, 2,21-methylenebis(6-t-
butyl-4-methylphenol), 4,41-butylidenebis(6-t-butyl-3-methylphenol), t
He5-trimethyl-2,4,6-tris(45-di-t
-butyl-4-hydroxybenzyl)benzene and tetrakis(methylene(45-cy t-'7'thi-4-
(hydroxy-hydrocinamate) methane, the last one being particularly preferred.

When the polymeric insulation is formed on the conductor by extrusion, it is preferred that the lubricant forms part of the insulation composition.

□ Lubricants containing fatty acids or their metal derivatives have traditionally been used. Lubricants are not only effective in the extrusion process, but also improve the stripping properties of wire insulation and facilitate the end user's work. The lubricant component constitutes an essential component of the polymer composition of the present invention. Addition of a combination of antimony trioxide and a halogenated flame retardant to a hydrated filler at the required concentration, in addition to a lubricatingly effective amount of a particular two-component lubricant, unexpectedly results in the present invention. It has been discovered that the crosslinked compositions of the present invention impart a completely unexpected degree of good flame resistance to the crosslinked compositions.

Calcium stearate has often been used as a lubricant for polymeric compositions such as those of North et al. However, lubricant compositions consisting of fatty acids such as lauric acid and alkylene-bis-amides such as ethylene-bis-steel, aramid, and especially antimony trioxide, f. ], it has been devised that when used in combination with a non-curing flame retardant, the crosslinked composition exhibits remarkable flame resistance.

The binary lubricant composition of the present invention consists of an 8 to 25 carbon fatty acid and an alkylene-bis-amide having the general formula:

(where R = divalent alkylene group with 2 to 8 carbon atoms; and R' = -C-R'', and R-rich is an aliphatic group with 8 to 25 carbon atoms.) The ratio to alkylene-bis-amide is from about 1:1 to about 1=6, preferably about 1:3 acid:alkylene-bis-amide.Preferably, the binary lubricant composition contains 25% lauric acid and 75% ethylene-bis-stearamide.The total amount of the binary lubricant composition is from about 101 to about 10 weight percent of the total polymer composition, preferably from about 0.5 to about 3. Weight percentage.

Two-component lubricant compositions are used in combination with antimony trioxide and nitrogenated flame retardants such as ethylene-bis-tetra-bromophthalimide, decarbromodiphenyl oxide, etc. in peroxide-cured polymeric compositions. At that time, an extremely effective C was invented. Antimony trioxide is included in an amount of about 2 to about 20 weight percent and preferably about 4 to about 1 weight percent of the total polymer composition, and the halogenated flame retardant is included in an amount of about 5 to about 3 weight percent.
The amount of polymer and filler in the compositions of the present invention can vary within a wide range, including 0 weight percent and preferably from about 8 to about 10 weight percent. It should be in the range of about 5 to 5.0 parts.

This small amount is insufficient to provide sufficient surface treatment, while too large an amount may affect some physical properties, such as elongation, properties of the extruded insulating material after crosslinking, etc. It has an undesirable shadow change.

Coatings, i.e., onto wires and cables, are 40 to 400 parts by weight or more (most preferably 125-150 parts by weight or more) of filler, 15 to 5.0 parts by weight of silane, and 100 parts by weight of polymer. Best results are obtained with extrusion.

There are many ways to form the compositions of the invention. However, in either case it is necessary to bring the filler and polymer into sufficiently intimate contact with the silane as the filler begins to be dispersed into the polymer. This condition can be achieved in internal mixing equipment such as a Banbury or Werner & Freidler extruder.

It is known in the art to combine the silane with the hydrated filler and the biopolymer component to obtain an intimate mixture of the essential components. Any processing equipment that can be used can be used.

In addition to the main components of the composition of the present invention, other additives, pigments, stabilizers, etc. may coexist as long as they do not interfere with crosslinking or adversely affect the desired properties. It is obvious that it is possible.

Such materials are present in very small proportions of the polymer, ranging from less than 10 parts, usually less than 5 parts. There are two reasons why it is undesirable to have significant amounts of other ingredients: firstly, the compositions of the invention have outstanding properties themselves; secondly, the presence of other fillers, e.g. Significant amounts only impair or upset the harmonious balance of nature.

Lubricants such as fatty acid soaps or their metal derivatives have been successfully used in the past to form insulation in conductors by extrusion. Such materials improve the stripping and stripping properties of wire insulation, and therefore make it easier for end users to strip the insulation from wires when calculating and terminating the wire. It is made to be removable. alkaline earth metal fatty acid soaps, the preferred soap being calcium stearate;
It has become customary to use a variety of acceptable soaps. Other typical examples of such lubricants include alkaline earth metal and aluminum salts of stearic acid, oleic acid, palmitic acid and other fatty acids used in the industry for this purpose, silicone oils, long chain However, it has now been discovered that the two-component lubricant system of the present invention not only acts as an effective lubricant, but also has increased flame resistance properties. In particular, it has been devised that it exhibits exceptional flame retardant properties when used in compound-curable polymeric compositions with halogenated flame retardants, antimony trioxide, and non-halogenated flame retardants. there were.

The following examples are intended to further illustrate embodiments of the invention.

The crosslinkable surface type coalescence composition shown in Table 1 uses calcium stearate as a lubricant (numbers in the table indicate parts by weight of the ingredients). 14AWGw of these compositions,
Extrusion molding onto the line Und@rwriters La
boratori@s F1am5Retardan
It was used as a sample for the tVW-1 (Vsrtical-Wire) test (ULFR-1). UL FR performed on samples containing calcium stearate
-1 test results are shown in Table 2.

Table 1 Sample number 1 2 5 4UE
630 100 100 100
100Ey 904 0 0
0 0 hydrated alumina 1
00 100 100 100 Silane A-
1722222 Aegerit@PilA antioxidant 2
2 2 2Saytex BT93 Brominated Flame Retardant 30 30 0
0Thermogard CPA
15 6 15 6 Calcium stearate 2 2
2 21: , : Lauric acid 0 , :, 1
0 0 0 Ethylene-bis-stearamide 0 0 0 0V
ulcup 40 KE (peroxide) 4.
25 4.25 4.25 4.25Sb101
0 0
0 05 6
7 8 9
j080 95 80 9
5 100 10020 5
20 5 0
0100 100 100 10
0 125 1252 2
2 2 2
22 2 2 2
2 230 30
30 50 50 20o
o o
o o.

15 15 6 6
15 102 2 ::
2 2 2 2 rin・: o o,,,o o
o.

o o o
o o.

4.25 4.25 4.25 4.25
4.25 4.25o o
o o o
.

Sample number 11 12 13UE 6
30 100 100 100E7
904 0 0 0 Hydrated Alumina 125 100
0 Silane A-172222 A@g@rits MA l! l! anti-inflammatory agent
2 2 2Saytsx Br35 Brominated flame retardant 20 20 30Thermog
rard CPA 6 15
15 Calcium stearate 2
2 2 Lauric acid
0 0 0 Ethylene-bis-stearamide 0 0 0 Vulcnp
40, E(i oxide) 4.25 4.
25 4.25Sb*Os
O001 (continued) 1 QOO100100100100100o
o o o
o.

0 0 100 100
100 1002 2
2 2 2 22
2 2 2
2 20 30
15 15 1 30so
o o
o o.

15 6 5 1
5 15 152
2 2 2 2
2o o
o o o
.

ooooo.

4.25 4.25 4.25 4.25
4.25 4.25o o
'o o o
.

Table 2 1 98 0 5 0 0 0 0 28
00 25 0
02 10S O3000002
0 2270 39715000 15500 0000 49870200 20000 33500 510! S O950 01600 0430 □ 6102 0”'6 0 0 0 0 3 0
0 21 0
07 103 0 0 4 0 0 10 0 0 0 0 4 0
OYes No Yes Fail OY@! l No Ye
sONONo N.

ONONONO Fail OYes NOYes OYes NOYes OYes No Ye++s
Fail OYss No Y
esO Yes No Yes
OYeI No Yes Fail OYes No Yes
ONONONO ONONO No Passed ONONONO ONONO N.

Seal・□・・：1 0 NO・j No NO Fail OYes No Yes
NONON10 0 Yes NOYes Fail ONONo N.

OYes No Yes8
108 2 0
60 0 20 0 7 8 9 95 0
2 00 15
6 0 6 3 10 98 7
5 010 4
50 3 0 11 99 0
4 265 0
062 0 012
99 0
G 40 0
0 0 0 95 15 98 5
5 010 0.0 0 0 10414
22 '15
56 0 88 0 0 0 0 0 0 Yes No
Yss Fail 0 0 Ys
s NOYe so 0 Ye
s No Yes 0
NONo No Fail 0
0 Ye8 NOYe so
0 NONONO o 0 Yes NOYe
II Fail 0 0 Yes
NOYeso 0 Yss
No Yes 0c Yes
NO, Yes Fail o
o NONONO o 0 NONON.

0 0 Yes No
Yes Fail 0 0 Ye
s No YeII0 0
Yes Yes @Ya mo 0
Yes No Yes
Fail 0 0 Yes No
Ysso 0 Yes Y
es' Ys+s0 0 NON
o NO Fail 0 0 YeI
YeI Yeso 0 Y
As is clear from the es NOYes test results,
Only two samples containing calcium stearate, /I65
and A19 passed the FR-1 flame resistance test. This result cannot be considered satisfactory.

Two combinations passed the test, but their compositions were similar to the other failing compositions, so if the FR-1 test were to be run again, the chances of reproducibly passing the test would be extremely slim. However, this composition cannot be accepted for practical use.

It was prepared using a two-component lubricant in combination with a halogenated flame retardant and antimony trioxide. The samples are shown in Table 5.

Table 3 UE650/651100 95100100100E
7904 0 5 0 0 0 Hydrated alumina 100 100
100 100 100 Silane A-1722
2222 Human egertte MA antioxidant 22
2 2 2Saytex BT93
30 50 50 0 30
FR300BA OOO500The
rmol(mrd CPA 15 15
15 15 15 Calcium stearate o o
o o.

1□1 Laurin Awakening α125 α125
α125 α125 0.25□ ・11; □ Ethylene-bis-stearamide α575 0.5
75 α375 α375 α75Vnl
cup90KE 4.25 425
4.25 4.25 4.25sb snow 0. o
o o o
.

25 26 27 28
29 30100 100
80 80 100 100
0 0 20 20
0 0100 100
100 100 100 1
002 2 2 2
2 22 2
2 2 2 2
50 0 30 0
30 250 30
0! 10 0
0ro 0
15 15 10
12.5o'lo o
o o.

,,j,.

Q, 25 nJ”m5 α25 Ll, 2
5 (125125・1″・1] 5 1 α75 α75 0.75 α7
5 0.75 α754.25
4,25 4.25 4.25 4
．． 25 4.2515 15
0 0 0 0Table 3
UL FR-1 testing was conducted on samples containing binary lubricant systems.

The results are shown in Table 4.

Table 4 20 103 0 9 3 0 0 14 0
00 4 3
021 99 0
0 6 0
0 3 0 0
0 0 30
022 95 0
6 0 00
23 0
00 15 0
025 94 0
5 0
0 o ss o
.

0 58 0
024 qy o go.

θ′2 16
00 3 0
025 105 0
25 000
19 0
00 6 0
0ONONONO passONONO NO ONONO N.

ONONONo Fail OYes No YesON
ONo N.

ONONo No Passed ONONo NO ONONo　　　　N.

OYes NOYes Fail OYes
No Y@10
Ys s No Y@s
ONo・No No Pass 1 “ONONON0 Mouth N0NoN.

ONONONO Passed ONONONO ONONO NO From these results, in the strict FR-1 exam, 2yrJjl
The sample with the binary lubricant system passed for only 50 hours, while the sample without the lubricant system passed for only 18 hours.
In addition, compared to samples 18 and 19 containing calcium stearate as a lubricant, sample 2 containing a binary lubricant system
It is clear that Nos. 2-30 have other desirable properties such as physical strength and elongation properties as shown in Table 5.

Table Sample number 18 19 22 23 2
4 Tensile strength psi 1880 1850 21
10 2470 2180 growth chi
210 240 200 250 2
00158℃ Tensile strength after 7 days psi 2060 1980 215
0 2500 2280 Growth %
150 140 160 170 1
5025 26 27 28
29! S.

Claims (1)

[Claims] 1. a) Copolymer of ethylene and c, -C, vinyl ester of aliphatic carboxylic acid, CI-C alkyl ester of acrylic acid, or C1-Cs alkyl ester of methacrylic acid. , b) 80 to 400 parts of hydrated (b) inorganic filler per 100 parts of copolymer, C) [14 to 8 parts of alkoxysilane per 100 parts of hydrated inorganic filler, and d) 8 to 25 parts of hydrated inorganic filler. fatty acids having 2 to 8 carbon atoms and alkylene-bis-stearamides having the general formula [(1 R is a divalent alkylene group having 2 to 8 carbon atoms, and R' is -〇-R'' (However, R
3 is an aliphatic group having 8 to 25 carbon atoms)
A crosslinkable polymeric composition having improved flame resistance comprising a binary lubricant system comprising: a halogenated flame retardant component; and optionally antimony trioxide. λ The binary lubricant system is about α1 to about 1° of the total polymer composition.
A composition according to claim 1, present in an amount of 0 weight percent. (5) The binary lubricant system is about α5 to about α10 of the total polymer composition.
A composition according to claim 2, wherein the composition is present in an amount of percent by weight. 4. The composition of claim 2 or 3, wherein the ratio of said fatty acid to said alkylene-bis-amide is from about 1=1 to about 1=6. 5. The composition of claim 4, wherein said ratio is about 1:3. k Composition 07 according to any one of claims 1 to 5, characterized in that the fatty acid is lauric acid, and the alkylene-bis-amide is ethylene-bis-amide.
7. The composition according to any one of claims 1 to 6, which is stearamide. 8. The composition of claim 6 or 7, wherein the ratio of lauric acid to ethylene-bis-stearamide is about 1:3. 9. Approximately 5 of the rogenated flame retardant factory polymer composition
The composition according to any one of claims 1 to 8, wherein the amount F is approximately 301N. 10. The composition according to claim 1, wherein the 1α halogenated flame retardant is ethylene-bisutetopromophthalimide or deca-bromodiphenyl oxide. 11. Antimony trioxide is present in an amount of about 2 to about 20 weight percent of the total polymer composition.
The composition according to any one of Items 1 to 10. 12. An electrical conductor covered with a single insulating layer comprising a crosslinkable polymeric composition according to any one of claims 1 to 11.