JPS58501235A - Flame retardant composition, method for producing the same, and wire and cable products thereof - 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] Flame retardant compositions, methods for their production and wire and cable products thereof 汰-”L-匁一”［ A number of compositions with exceptional properties have already been manufactured using patented technology. It is. One such composition is disclosed in U.S. Pat. Protected by No. 4.247°446. This composition has excellent properties However, both in terms of material composition and material processing, and also as wire insulation. The cost is also relatively high for the final product applied. U.S. Patent No. 4,123 , 586 and 4,247,446. One of the reasons for this is that it is difficult to achieve a unique combination of properties, making processing costs relatively high. This is because the ingredients must be combined in a unique manner in order to achieve this.

Therefore, while achieving the desired combination of excellent properties, it is also The goal of the industry is to achieve even lower costs in terms of materials and processing technology. It was. This is because the ease of processing materials greatly affects the cost of the final product. be. For example, as pointed out in U.S. Patent No. 4,123,586, The flame retardant components are separately processed and prepared by the method described in Patent No. 4.209.566. Until now, these conditions have been considered essential.

U.S. Patent Nos. 4.123.586 and 4.247. .

No. 446's high specification material processing is based on the flame retardant components of U.S. Pat. Compound production, including machining, based on a given labor and equipment combination. This leads to a reduction in production rates and therefore to an increase in costs. This production rate is actually Although half the production rate according to the invention, U.S. Pat. 247.446 and the relatively high cost and high specification materials of U.S. Pat. 209.566 is suitable for its processing.

Another area of interest in the industry is lower cost wire or cable Not only is it easier to process into the final insulating layer on the Qualitative requirements, e.g. various testing bodies, e.g. Underwriters Laboratories - Established by (IJ derwriters L laboratory) Find a composition that also meets the standard requirements, such as the standard conditions of the VW-I test. Is Rukoto.

U.S. Patent Nos. 4,123,586, 4.247,446 and 4.209 ．． No. 566 is assigned to the same assignee as this application.

of Accordingly, one object of the present invention is to provide superior flame retardancy and superior wiping at relatively low cost. An object of the present invention is to provide an insulating composition having both high and high insulating properties, and a method for producing the same. be.

Another object of the invention is the processing, pelletizing and direct wire insulation into wires. To provide a composition as described in the first object, which is relatively easy to form. It is in.

Another purpose is its exceptional flame retardant properties and good physical properties to apply to wires. In addition, it is extremely suitable for use as a wire insulator. The object is to provide compositions that also have desirable electrical properties at relatively low cost.

Still another object of the present invention is to have high flame retardancy and use a 35 kg cable as an electric power cable. with suitable properties for use at voltages up to and above Our objective is to provide novel cable products insulated with this composition. .

Another object of the invention is to be suitable for use in wet and humid environments and to To provide novel insulating compositions that sometimes have good flame retardant properties and are relatively low cost. There are many things.

Another purpose is to be suitable for use in nuclear applications and in particular to comply with IEEE- 323 and IEEE-383. It is about providing.

4 The secondary objective is to provide a composition that passes the LOCA test at a relatively low cost. include.

Another object of the invention is that the cable is connected to petroleum products, such as in oil well applications or locomotive applications. Under LIL standard conditions for applications up to and above 105°C in exposed environments The object of the present invention is to provide a composition that can be used.

Another goal is to provide adequate performance with relatively thin wall pressures, on the order of 5 or 10 mils, and to Compositions suitable for use in electronic wire type applications and wires formed therefrom Our goal is to provide products.

Yet another object of the invention is to have a dielectric strength as high as 1300 volts/mil. An object of the present invention is to provide an insulating composition.

Another purpose is to perform UL VW-1 testing on unshielded power cable structures. and 100 hour hour test as specified in the UL-1072 test procedure. The object of the present invention is to provide an insulating composition that passes the test.

Other objectives are some self-evident and some pointed out in the description that follows.

Brief description of the drawing The drawing shows an insulated conductor with flexible polyolefin insulation around the metal member. FIG.

Summary of the invention To achieve the object of the present invention, it is first necessary to prepare a polyolefin polymer with a significant proportion of Brominated flame retardant; considerable proportion of minerals 5 Patent 858-501235 (4) Flame retardant , e.g. antimony oxide; and in combination with a significant proportion of siliconized clay material. , and these ingredients are further mixed with relatively small proportions of lead stabilizer compounds and antioxidants. An insulating composition is produced by combining with a material. First, the various ingredients mentioned above were combined. After that, to this 10th coarse combination, but at a lower temperature, silicone oil and organic peroxide are added. Add a second combination of substances. Following the second addition, this material was added to wire 1. let

Peroxide components can be removed if necessary, and radiation The composition can be more crosslinked.

DESCRIPTION OF THE PREFERRED EMBODIMENT The polyolefin used in the present invention refers to polyethylene as a preferred component; The olefin can also be a copolymer of ethylene, such as ethylene-ethyl acrylate. rate, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, - terpolymers and quadrepolymers, such as EPDM, Not limited to these. Polyolefins can also be high density or low density polyethylene. It may be any type of material, or it may be a polyallomer. .

Organic halogenated flame retardant is decabromodiphenyl oxide 3 aytech C0 Echi sold through commercial channels from rpOratiOn under the product name BT-93. Renbis (tetrabromophthalimide) or less brominated diphenyl bromine It can also be an oxide. More generally, stable organohalogenated flame retardants , for example, products from Hooker Chen+1cal Corporation. Chlorinated flame retardants that can be used manually through commercial channels can be used with name Q echlorane. .

The antimony oxide flame retardant used in the present invention is a conventional or standard compound powder. .

IJ:l->The treated clay is Freeort Kaolion Compa Commercial set sold by NY under the product name T ranslink37 clay It can be made into a product. or a U.S. patent assigned to the same assignee as this application. Similar clay compositions as taught in Lamb 2 of No. 3.148.1g9 It can be done.

The compositions of the present invention may optionally include dibasic lead phthalate compositions or components. This ingredient has a lead content approximately equal to the lead content of dibasic lead phthalate. or more, any organolead compound. For example, low volatility Although other organic compounds that provide suitable stabilizing properties can be used, Basic lead phthalate is a preferred compound for this component. Stabilization is achieved by a lead compound. This means that free halogens can be scavenged from the product.

The antioxidant component preferably includes a low cost antioxidant, such as commercially available frectol. Frectol H, commercially available Santo White Crystals towhite crystals) or used in specific examples in the construction table below. There are combinations such as The performance temperature of the composition is also at a relatively low level of about 105°C. deer However, if performance at even higher temperatures is desired, the general rules listed in connection with Table V may be used. Such high-temperature performance can be achieved by incorporating antioxidants. Wear.

Next, considering the silicone oil component, silicone oil is 9.566.

As mentioned above, peroxide curing agents decompose at high temperatures higher than the standard mixing temperature. In other words, it can be an organic peroxide that generates free radicals, and it can be used as an organic peroxide that generates free radicals. It is better to use sea urchin dicumyl peroxide. Alternatively, the cost is dicumyl peroxy Although it is more expensive than CID, it uses materials sold under the product name Vul-Cup R. It's okay. Such organic peroxides are widely used in the industry and patent publications related to this technical field. known in the art, some of which are described in the above patents, which are cited herein by reference. Ru.

Similar to the dibasic lead phthalate, silicone gum can be used as an optional ingredient; Therefore, it was included in Example 1 below. The novel composition of the present invention has A pending U.S. patent application for silicone gum that has been granted in the same application as this application No. 196.989 (filed October 14, 1980). pending U.S. Patent Application No. 196°989 is a pending U.S. patent application (Attorney Case No. 41WC-2135, 1-July 21, 981 @), the reference text of the present invention make an offering The advantages pointed out in this pending application also apply to the compositions of the present invention. can get.

119-L Table 1 lists a set of ingredients and the proportions of these ingredients (expressed in parts by weight). Both preferred concentration ranges and usable concentration ranges of various components are shown.

The first seven ingredients as listed in the construction table were prepared as follows: Banbury (Ba nbury) Complete with mixer. Mix now.

The seven ingredients are first mixed in a high-power mixer, such as a Panbali mixer, at a temperature of approximately 150°F. Put it in. The mixing action of the high-power mixer generates heat in the composition, increasing the composition temperature during mixing. Measure. Once the apparatus temperature reaches approximately 270°F, the composition is Drop from the power mixer. The heat received by the composition is the heat of mixing, and for the purpose of this temperature increase There is no need to apply external heat.

After removing a batch of material exhibiting a tip temperature of approximately 280-290°F from the high-intensity mixer. , roll kneading on a plastic roll machine. Material on roll machine for plastics Wrap it into a band and take it out as a sheet.

The sheet material is then coated with liquid silicone oil and an oxidized crosslinker. In particular, it is combined with a mixture of dicumyl peroxide. This formulation contains a peroxide crosslinker. It is carried out at a low temperature lower than the melting temperature. The composition at a temperature of about 220'F up to 240°F. Mix with a powerful mixer.

] Following the introduction of silicone oil and peroxide crosslinker into the compound, the composition is Knead the plastic roll again to form a sheet, then cut the sheet into strips. , and then pelletized suitable for later use in an extruder.

Polyethylene 100 100 Decabromodiphenyl 10-50 20-40 oxide Antimony oxide 3-30 10-20 1 silicone treated clay 5-50 1 0-30 Dibasic lead phthalate 0-20 5-10 Silicone gum 0-20 0-10 7 Rector H*Ne 0-10 1-5 Santo White O-50-3 crystals book book Silicone oil ＊＊＊＊ 1-5 1-3 Peroxide crosslinking agent 1-5 2-5 (Dicumyl peroxide) 0 Manufactured in accordance with the teachings of this U.S. Pat. No. 3,148,169, column 2, or similar methods. .

*F 1ectolH is polymerized 1,2-dihydro-2゜2,4-trimethylene Luchinorin brand name ＊　＊　＊ S antwhite Ct rystals are 4,4′-chi Trade name of Obis-(-6-t-butyl-cresol).

**Prison* U.S. Patent Nos. 4.123.586 and 4°247.446 1. .

Silicone oils or similar compositions as described in No.

Branch 19-1 The composition thus prepared was wrapped around #14AWG wire with a 30 mil insulation sheath. It was extruded as Q. This composition is cross-linked by heating the wire insulation under pressure. I made a bridge.

The cross-linked composition has a high tensile test of over 2100 psi and a high tensile test of over 400%. It has very good physical properties for use as wire insulation, including high elongation values. It has been demonstrated that

The data are tabulated and shown in Table ■, following the method of the present invention as described above. The results of a series of standard tests performed on the formed wire insulation are shown.

1 Superintendent “Nyo” Exam JLL 2 mistakes Structure #14 solid bare wire, Wall thickness 0.03 inch Test piece identification code IQ-92-44-1 Initial tensile strength, psi 2143 Initial elongation, % 447 High temperature modulus book 88.5 Heat aging based on standard UL test procedures 7 days questions 121℃, %RT/%RE*ne 103/98136℃, %RT/%RE 100/93158℃, %RT/%RE 95/7297℃ 30 days, %RT/%RE 103/9860 days, 92/76 90 days, 105/94 120th, 102/83 150 days, 100/82 113℃ 30th, n 105/79 12 60th, 103/85 Oxygen index by standard UL test Oxygen concentration % display 29.5 Passed VW-1 by standard UL test Low temperature bending, -65℃, 1 hour, passed #2 ASTM oil, 70℃, 4 hours Swelling rate % 4.6 %RT/%RE book* 86/92 42 hour air cylinder, %RT/%RE 102/87 (standard LIL test) Conductor corrosion by standard tJL test Passed at 121℃ for 7 days Passed at 136℃ for 7 days Dielectric strength, V/mil 1382 13 Patent 1985-501235 (6) According to IJL and l CEA standard test Rapid voltage increase at 500 volts/second I Insulation resistance by CEA standard test constant 82.765 According to UL and I CEA standard tests EM-60 water test (75℃) 1st: Relative permittivity 2.35 Dielectric constant % at 80■/mil 0.93 Stability factor 0.04 7th: Relative permittivity 2.34 Dielectric constant % at 80V/mil 0.6614 days: Relative permittivity 2.35 Dielectric constant % at 80V/mil 0.57 Stability factor 0.02 Increase rate of relative permittivity% 1-14 days 0 7-14 days 0.43 4 IEEE383 and 323 compliance Simulates 40 year thermal life After heat aging, 33 days LOCA service 220 megaland before the cycle. Exposure to gamma rays, then to 2.4 ■/min Passed hipot* 100% of initial length at 150℃ The tensile strength was measured in psi.

**%RT/%RE = Initial tensile strength retention rate (%) and initial elongation retention rate (%) Referring to the experimental results reported in Table ■ above, wires of crosslinked compositions and A number of important considerations can be made regarding its effectiveness as a cable insulator.

The first thing to notice is that, to the best of the applicant's knowledge, it exhibits VW-1 characteristics (VW- 1 test) for use as an insulator on unshielded cables. Until now, there has been no possibility of passing the cut-and-bend test.

Conventional cables with an insulating layer that pass the VW-1 test have a shielding sheath. If I didn't hit it, I wouldn't have passed the U-bend test. Therefore, the present insulating composition and this Cables formed from the composition are entirely new and unique.

Unique feature of unshielded cables that pass both U-bend and VW-1 tests In addition to the combination of The results show that the new composition of the invention has an oxygen index of 29.5, which The value of is extremely high for compositions with other combinations of properties.

Another thing to notice about the data in Table ■ is that the dielectric strength is low for a flame-retardant material. , in particular a VW-”! grade material, and more particularly the material has an oxygen index of 29.5. As a material, it is always expensive. Due to the characteristics of such a combination, the present invention The new composition has become highly suitable for use in electrical power cables. Electric phone This new composition is particularly suitable for use in bulls due to its relatively low cost and This is because power cables insulated with new compositions have a relatively low cost. Ru.

The low cost of this new composition is due in part to the ease of processing of this composition. Originates from For example, even though the resulting hun pound is completely unique and novel, ), standard equipment and standard processing steps can be employed.

As can be seen from Table ■, the results obtained from the heat aging test at 113°C are The physical properties as a function, especially the tensile and elongation properties, deteriorate very slowly. It proves that. UL heat aging to ensure the suitability of the composition for use at 105°C Tests include heat aging at 113℃ for 30.60 days and 90 days. There should be no significant deterioration in properties. The results in Table 2 show that the new composition of the present invention Not only can you easily pass the UL test, but the data in Table ■16 in 90 days even after 120 and 150 days it shows only a slight decrease in properties. This has proven to be superior to the LIL test standards.

From Table ■, high dielectric strength allows for thin-walled insulators of 10 mils or even 5 mils. Therefore, it is clear that products made of the insulator of the present invention can be used for electronic applications. It is. Furthermore, since the composition of the present invention is easy to process, it can be used for electronic wires. Manufacturing becomes practical.

fi #14 AWG conductor insulated with 30 mil insulation.

A 7-conductor control cable was manufactured using 7 lands. Individual insulated conductors are shown in the construction table. It was the same as that used above to conduct the tests reported in. Then the control cable A combustion test was conducted. The following data were obtained.

7 conductor control cable structure Passed IEE with 210.0OOBTU E Vertical flame test Branch I9 - Destination Cable articles are made using compositions made as described in connection with the above schedule. Built. The cable was made of #2 AWG copper conductor. Preferred compositions in Table 1 above Form a 205 mil thick insulation layer by blending and extruding it around the conductor. and then the compound is activated by peroxide 17 Patent 558-501235 The cable is heated to a temperature higher than (7) degrees and the cable is heated to a temperature well known in the industry. Pressure was applied in this way.

The cable products manufactured as described above were then subjected to a number of tests. The test results are as follows Report in Table ■.

Soaked in water at 75°C for 14 days, then The cable is subjected to a U-bend test rate of 15 km and a passing bolt for 350 hours. Soak the formed cable in water. Passed the dry U-bend test without soaking. Used for 100 hours at 20 kilovolts. To this example cable with a wall thickness of 205 mils Vertical flame of 210,0OOBTLI, test amount passed *U-bend test is shielded The structure of electric power cables is specified as LIL-1072 trial procedure. There is.

The above results, especially those listed in Table ①, were used at a standard operating temperature of approximately 105°C. Insulating compositions that can be used have also been reported. The actual working temperature of the composition is Although it can be higher than 105°C, the reference to 105°C here is based on industry-recognized standards. This is because it is the standard for the LIL standard.

8 As mentioned above, the composition of the present invention satisfies industry standards and can be used as an insulating composition at 105°C. Fully functional.

However, the composition inherently functions at higher temperatures and higher temperature grades. You can also accomplish this. For example, compositions of the present invention may be used at temperatures of 125°C and above. This temperature of 125°C is also the standard tJL temperature class for insulating compositions. be. To bring the composition as described above into acid interaction with the 125°C composition, The following combination of antioxidants is incorporated into the composition.

Polyethylene 100 100 Brominated aromatic compound 10-50 20-40 Antimony oxide 3-30 10 -20 silicone treated clay 5-50 10-30 dibasic lead phthalate 0- 20 5-10 silicone gum 0-20 0-10 0-1O2* 1-10 1-5 Ir(llanOX1010** 1-5 0-3 Silicone oil 1-5 1- 3 Peroxide crosslinking agent 1-5 2-5 dicumyl peroxide Book Zinc Salt of Mercaptoimidazole This sterically hindered di-t-butylphenol 9 The components labeled ``book'' and ``woody'' are described in U.S. Pat. As described in No. 260.661.

In other words, if the insulating composition is used at higher service temperatures, it will typically meet the requirements listed in Table 7. If the antioxidant component is high, it can be used in large quantities in the combinations listed in Table temperature shall be guaranteed.

Specifically, if you want a working temperature of 125℃, use the lower value listed in Table 7. ZMS-2 component and lrllanOX component in the ratio or proportion as specified in the range. should be used in the higher concentration range listed for the inhibitor. It would be possible to achieve higher operating temperatures such as

As previously mentioned, the peroxide component of the composition may be omitted, in which case the high energy energy radiation, such as high-energy electrons, by methods well known in the art. The coating composition can be crosslinked and cured.

As shown in the drawings, the center conductor 12 is surrounded by an insulating layer 1 manufactured according to the present invention. 4 is formed. The insulating layer 14 can be in either a curable state or a curable state. It's okay.

20 The hardened insulating layer can also be hardened chemically or by high-energy radiation. can be made into The product shown is an insulated conductor 10 whose conductors are as shown. It can be solid or stranded.

Although the invention has been described with respect to several specific embodiments, many modifications and variations are possible and the invention has been described with reference to several specific embodiments. It is desired to cover all modifications that fall within the spirit of the invention.

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Claims (1)

[Claims] 1. The following ingredients: Ingredient range Decabromodiphenyl oxide 10-50 antimony oxide 3-30 Silicone treated clay 5-50 Dibasic lead phthalate 0-20 Sunwhite Crystals O-5 Silicone oil 1-5 A crosslinkable composition having properties suitable as an insulating material. 2. A crosslinked composite/acid according to claim 1. 3. A cable coated with the composition according to claim 1. 4. A cable insulated with the composition according to claim 2. Decabromodiphenyl oxide 10-50 antimony oxide 3-30 Silicone treated clay 5-50 Dibasic lead phthalate 0-20 Silicone gum o-20 2 Frektor H0-10 Santo White Crystals 0-5 Silicone Oil 1-5 Peroxide crosslinking agent 1-5 (Dicumyl peroxide) A crosslinkable composition having suitable insulating properties. 6. The cured composition according to claim 5. 7. An electrical appliance having a layer of the composition according to claim 5 thereon. 8. A cable product having a coating of the composition according to claim 5 therearound. 9. An electrical appliance insulated with the composition according to claim 6. 10. Electronic wire insulated to a thickness of 5 mils or more with the composition according to claim 2. I don't like it. 11. High voltage insulated to a thickness of 30 mils or more with the composition according to claim 2. cable. 12. The following ingredients: 1--1 LJL Polyethylene 100 Decabromodiphenyl oxide 20-40 Antimony oxide 10-20 Silicone treated clay 10-30 Dibasic lead phthalate 5-10 Silicone gum O-10 23 Frektor H1-5 Santo White Crystals O~3 Silicone Oil 1-3 A crosslinkable composition having properties suitable as an insulating material. 13. The crosslinked composition according to claim 12. 14. A cable coated with the composition according to claim 12. 15. A cable insulated with the composition according to claim 13. 16, Ash--” L ILJL Polyethylene 100 Decabromodiphenyl oxide 20-40 Antimony oxide 10-20 Silicone treated clay 10-30 Dibasic lead phthalate 5-10 Silicone gum 0-10 7 Lectol H1-5 Santo White Crystals 0-3 Silicone Oil 1-3 Peroxide crosslinking agent 2-5 (Dicumyl peroxide) A crosslinkable composition having suitable insulating properties. 17. The cured composition according to claim 16. 24 *eQ58-501235 (2, composition according to claim 17) electrical appliances that have a layer of 19. A cable product having a coating of the composition according to claim 18 therearound. 20. An electrical product insulated with the composition according to claim 19. 21. Electronic use insulated to a thickness of 5 mil or more with the composition according to claim 13. wire. 22, high voltage insulated to a thickness of 30 mils or more with the composition according to claim 13. pressure cable. 23, Roasted L ILJL Polyolefin 100 Brominated aromatic compound 10-50 Antimony oxide 3-30 Silicone treated clay 5-50 Dibasic lead phthalate 0-20 Silicone gum 0-20 Zinc salt of mercaptoimidazole 1-10 sterically hindered di-t-butylphenol 1-5 Silicone oil 1-5 A curable polyolefin polymer compound of suitable insulating properties. 24. The crosslinked composition according to claim 23. 25. Conductive 5 insulated with the composition according to claim 24 Sex items. 26, 1--1 1LJL Polyolefin 100 Brominated aromatic compound 10-50 Antimony oxide 3-30 Silicone treated clay 5-50 Dibasic lead phthalate 0-20 Silicone gum 0-20 Zinc salt of mercaptoimidazole 1-10 sterically hindered di-t-butylphenol 1-5 Silicone oil 1-5 Peroxide crosslinking agent 1-5 dicumyl peroxide A curable polyolefin polymer compound of suitable insulating properties. 27. The crosslinked composition according to claim 26. 28. A cable insulated with the composition according to claim 26. 29, Ash-jL Range-” Polyethylene 100 Brominated aromatic compound 20-40 Antimony oxide 10-20 Silicone treated clay 10-30 Dibasic lead phthalate 5-10 6 Irganox 1011 0-3 Silicone oil 1-3 A curable polyolefin polymer compound of suitable insulating properties. 30. The crosslinked composition according to claim 29. 31. Ku brominated aromatic compound insulated with the composition according to claim 29 20-40 Antimony oxide 10-20 Silicone treated clay 10-30 Dibasic lead phthalate 5-10 Silicone gum 0-10 Zinc salt of mercaptoimidazole 1-5 sterically hindered di-t-butylphenol O-3 silicone oil 1-3 Peroxide crosslinking agent 2-5 dicumyl peroxide A curable ethylene-based polymer compound of suitable insulating properties. 33. The crosslinked composition according to claim 32. 2, A cable insulated with the composition of claim 32.