KR20010024512A - Polyvinyl chloride based plenum cable compositions - Google Patents

Abstract

The present invention comprises poly (vinyl chloride) resins, chlorinated poly (vinyl chloride) resins or mixtures thereof, polyhaloalkylphosphates and / or polyhaloalkylthiophosphate flame retardants of formula (I) and compatibilizers (anti-spills) A flame retardant composition relates.

Formula I

In Formula I above,

M is sulfur or oxygen,

X ¹ , X ² and X ³ are each independently halogen selected from the group consisting of chlorine and bromine.

Preferably the composition comprises a flame retardant and other halogenating additive sufficient to provide a composition having a halogen content of about 2.0% by weight more than the halogen content of the poly (vinyl chloride) resin, chlorinated poly (vinyl chloride) resin or mixtures thereof. . Such compositions can be used with smaller amounts of flame retardants to meet flame retardancy standards, thereby reducing the cost of the compositions and formulating them for easier use in wire and cable manufacturing processes.

Description

Polyvinyl chloride based plenum cable compositions

PVC (polyvinyl chloride) and CPVC (chlorinated polyvinyl chloride) are typically used widely for wire insulation and cable sheathing, with plasticizers so that they can be processed as flexible materials. Typically the composition also includes a heat stabilizer.

One particular application that requires enhanced flame resistance and smoke resistance is the manufacture of plenum cables. Plenum cables are electrical cables installed in confined spaces, such as air handling plenums in buildings, to provide electrical connections (both sound and data) between different parts of the building.

The plenum cable consists of a plurality of conductors protected by a first insulating layer, which provides electrical / signal isolation between the proximity conductor and the physical protection in which the optical fiber is used. The first insulator can be PVC, fluorinated polymer, eg FEP (e.g. Teflon FEP, DuPont), PVDF (e.g. Kynar PVDF, Penwalt) and E-CTFE (e.g. Halar , Allied Chemical Co.) or polyolefins such as polypropylene or peroxide cured polyethylene, which may further contain a flame retardant. The perimeter of the conductor is a jacket, which provides additional protection and helps to identify and install. The jacket of the plenum cable is typically a suitably formulated vinyl chloride resin or fluoropolymer.

Unmodified PVC decomposes at about 150 ° C. and is thermally unstable, but has relatively good flame retardancy. However, the plasticizers necessary to overcome their stiffness and allow them to be processed as flexible materials increase their flammability, especially when used at higher levels. In addition, the combustion of PVC generates a large amount of smoke, which not only contains toxic substances but also limits its visibility.

In order to prevent the spread of smoke and flames throughout the building through the plenum, the details of the plenum cable are particularly stringent in terms of flame resistance and smoke resistance. The most commonly used standard for measuring the tolerance of cable formulations for use in plenums is the UL 910 (Underwriters Laboratory Specification) test, from which flame and flame resistance are measured.

Vinyl halide polymers may be formulated into compositions that have passed the UL 910 test. The formulations are typically complex and contain most or all of the following types of additives: flame retardant plasticizers, nonflammable plasticizers, additional flame retardants, smoke inhibitors, stabilizers, antioxidants, lubricants, pigments, fillers and other additives.

Flame retardant wire insulator and cable jacket compositions comprising various additive mixtures are described, for example, in US Patent 4,670,494 (Sememza, Jr.), US Patent 5,227,417 (Kroushl, III), US Patent 5,036,121 (Coaker) And US Pat. No. 4,246,158 (Popp). Flame retardant additives such as antimony trioxide, antimony pentoxide, sodium antimonate, alumina trihydrate, zinc borate, zinc hydroxytartrate and zinc stannate have been used. Smoke inhibitors include compounds such as molybdenum trioxide, ammonium molybdate, magnesium oxide, zinc oxide, zinc molybdate and ferrocene. Plasticizers include compounds such as tricresyl phosphate, tricylenyl phosphate, iso-decyl diphenyl phosphate and chlorinated paraffins. Fillers such as magnesium hydroxide, magnesium carbonate, huntite and hydromagnesite, as well as calcium carbonate and electrical grade clays (which can be included to achieve specific physical and electrical properties) are also described.

Compositions that have passed the UL 910 test contain large amounts of flame retardant plasticizers (brominated phthalate esters) and fuming inhibitors (ammonium palmybdate). The use of such additives at high levels makes the composition thermally unstable and relatively expensive during processing. The wire manufacturer lowers its extrusion temperature to prevent degradation, which can reduce production throughput. As a result, the flame resistance and the smoke resistance of the composition which pass the UL 910 test requirements and are relatively easy to process without being ridiculously expensive are required.

The present invention relates to compositions having flame retardant properties, which not only reduce smoke during combustion but also improve stability and processing properties. In particular, the present invention relates to a flame retardant poly (vinyl chloride) composition, which is particularly applicable to the sheathing of a first insulator and a plenum cable.

The present invention

Poly (vinyl chloride) resin, chlorinated poly (vinyl chloride) resin or mixtures thereof (a),

At least one flame retardant (b)

A flame retardant low smoke composition comprising the compatibilizer (c).

In Formula I above,

M is sulfur or oxygen,

X ¹ , X ² and X ³ are each independently halogen selected from the group consisting of chlorine and bromine.

Such compositions which are excellent in flame resistance and smoke resistance are based on vinyl halide resins such as poly (vinyl chloride) (PVC) and chlorinated poly (vinyl chloride) (CPVC), copolymers thereof and blends thereof. The composition can be prepared by incorporating a flame retardant into a vinyl halide resin. Flame retardants are not completely compatible with PVC and / or CPVC resins and may be exuded from the composition when exposed to elevated temperatures, but mixing an appropriate amount of compatibilizer may provide a composition that does not spill the flame retardant.

Preferred compositions include about 5 to 15 phr of vinyl halide resin (PVC and / or CPVC), polyhaloalkyl phosphate and / or polyhaloalkylthiophosphate phosphate flame retardant (per 100 parts of vinyl halide resin) and about 1 to 8 phr of a compatibilizer. do. In a more preferred embodiment, this mixture further comprises boron oxide or boron 2 to 10 phr containing salts.

In one embodiment the invention comprises poly (vinyl chloride) resins, chlorinated poly (vinyl chloride) resins or mixtures thereof, polyhaloalkylphosphates of formula I and / or polyhaloalkylthiophosphate flame retardants and compatibilizers Composition. More preferably, the composition comprises boron oxide and / or one or more boron containing salts.

Vinyl halide resins include vinyl halide homopolymers (ie, PVC), grafts or random copolymers of PVC with other comonomers, and blends of homopolymers and copolymers. This includes poly (vinyl chloride) as well as chlorinated poly (vinyl chloride) containing 58 to 73% by weight of chlorine. In addition, the functional fragments used for copolymerization are those which affect the processability and physical properties of the resin.

Flame retardants include the polyhaloalkylphosphates and polyhaloalkylthiophosphates mentioned. Polyhaloalkyl phosphates are preferred. Preferred polyhaloalkylphosphates include tris- (trichloroneopentyl) phosphate, tris- (dichlorobromoneopentyl) phosphate, tris- (dibromochloro neopentyl) phosphate and tris- (tribromoneopentyl) phosphate to be. Most preferred halogenated flame retardants are tris- (tribromoneopentyl) phosphates.

The polyhaloalkylphosphate and / or polyhaloalkylthiophosphate flame retardant is incorporated into the composition in an amount sufficient to impart the desired flame retardancy to the composition. This amount varies depending on the degree of flame retardancy required for the intended application and the amount of other flame retardants (especially flame retardant plasticizers) present. It also depends on variables related to the application, such as the manufacture of the cable, the number of conductors and the like.

Generally, the amount of flame retardant required is, in addition to the other additives present in the composition, an amount that increases the halogen content of the composition by at least about 2% by weight above the halogen content of the vinyl halide resin used in the composition. For example, poly (vinyl chloride) having about 56.7% by weight of halogen requires a flame retardant sufficient to increase the total halogen content of the flame retardant containing composition to at least about 58.7% by weight and, if present, other halogenated additives.

The maximum amount of flame retardant added is recorded for economical and practical considerations, but generally does not exceed the amount providing additionally about 7% by weight of halogen (of the total weight of the composition). The preferred range is about 2.7 to about 4.0 weight percent of additional halogen, i.e., the composition has a halogen content that is greater than the halogen content of the poly (vinyl chloride) resin, chlorinated poly (vinyl chloride) resin or mixtures thereof used to form the composition. From about 2.7 to about 4.0% by weight sufficient flame retardant and other halogenation additives to provide a composition.

The composition also includes a compatibilizer that acts as a spill prevention agent. Compatibilizers, which may also be referred to as runoff agents, are additives that reduce the tendency of polyhaloalkyl phosphate and / or polyhaloalkylthiophosphate flame retardants to flow out of the resin. Useful reagents are reagents that enhance the compatibility of the components of the composition. Typically, the compatibilizer or anti-spill agent is during the accelerated aging, ie, heating the sample of the composition in an air circulation oven at 100 ° C. for at least two days, preferably at least three days, Delay (chalking) Preferably, the compatibilizer prevents the outflow of any significant amount of flame retardant during the processing and storage period of the composition.

A wide range of chemical compounds are potentially useful as compatibilizers. Copolymers of ethylene and vinyl acetate, terpolymers of ethylene, vinyl acetate and carbon monoxide, chlorinated polyethylene, vinyl chloride / ethylene copolymers and thermoplastic polyurethanes are typical. Since brominated phosphates tend to bleed out of vinyl halide polymers, brominated phosphate esters cannot be compatibilizers. Phosphate esters such as triaryl phosphate and aryl-alkyl phosphates are useful as plasticizers but do not act as compatibilizers in the compositions.

Preferred compatibilizers are the softeners currently used as part of PVC-based compositions. In the art of PVC formulations, the term "softener" is described as an additive that enhances the low temperature flexibility and elongation of the blended polymer. Useful compounds are copolymers of ethylene with vinyl acetate, such as Ultrathene (trade name, US Industrial Chemicals) or Elvax (Trade name: DuPont), terpolymers of ethylene, vinyl acetate or n-butyl acrylate and carbon monoxide [e.g. Elvaloy (Trade name, DuPont)], chlorinated polyethylene [e.g. Tyrin (trade name, DuPont-Dow)], vinyl chloride / ethylene copolymer and thermoplastic polyurethane [e.g. Estane (trade name, BF Goodrich)] or Mixtures thereof.

Preferably the composition comprises a compatibilizer sufficient to reduce the outflow of the phosphate flame retardant to the desired level or to completely prevent outflow. In general, the weight ratio of the compatibilizer to the halogenated flame retardant ranges from 0.1: 1 to 2.0: 1.

The composition preferably further comprises boron oxide or a boron containing salt. Preferred boron salts / oxides are zinc borate, calcium metaborate, barium metaborate, calcium pyroborate, potassium tetraborate, boron oxide, boric acid and ammonium pentaborate. The term zinc borate refers to various hydrate forms and anhydride forms thereof, such as 4ZnO.6B ₂ O ₃ .7H ₂ O, 2ZnO.2B ₂ O ₃ .3H ₂ O, 4ZnO.B ₂ O ₃ .H ₂ O and 2ZnO.3B. ₂ O ₃ ). These boron salts / oxides can be used individually or as a blend. Most preferred boron salt is zinc borate. The amount of boron salt / oxide incorporated into the polymer is generally proportional to the amount of polyhaloalkylphosphate and / or polyhaloalkylthiophosphate flame retardant present. The weight ratio of the boron compound to the weight ratio of the flame retardant is preferably 0.1: 1 to 1.0: 1.

The composition preferably also comprises an antioxidant or stabilizer. Such compounds are known in the art of plenum cable formulations. The above compounds in such compositions increase the degree of protection of the flame retardant, which reduces the tendency of degradation of the flame retardant during polymer preparation or processing.

The compositions may also contain polymer stabilizers, flame retardant synergists, fuming inhibitors, plasticizers, functional fillers and processing aids, which are well known in the art. Polymer stabilizers are based on lead and mixed metal soaps. Flame retardant synergists are additives known to enhance the effect of halogen containing flame retardant additives such as antimony pentoxide, antimony trioxide and sodium antimonate.

Smoke inhibitors are additives that alter the decomposition pathway of a polymer to produce char instead of smoke upon contact with heat or flame. Examples are ammonium molybdate, molybdenum oxide, ammonium molybdate, zinc molybdate, zinc stannate, zinc hydroxytartrate, copper oxalate, ferrocene, magnesium oxide and zinc oxide.

Conventional plenum cable formulations typically contain 10 to 20% by weight fuming inhibitors. However, these high levels of fuming inhibitors reduce the stability of the composition, reduce the cable manufacturing speed, and adversely affect the physical properties of the cable, in particular its resistivity, low temperature flexibility and color. The composition can be formulated with less or even no fuming inhibitor. Compositions that do not contain smoke inhibitors may be acceptable in low smoke applications, but may not meet more stringent test requirements, such as the UL910 test.

Preferably the composition comprises about 8 to about 15 phr smoke inhibitor. If a smoke inhibitor is present, the preferred smoke inhibitor is ammonium palmybdate. Such preferred compositions, including reduced amounts of fuming inhibitors, are less expensive, easier to process, and offer the opportunity to incorporate other additives to produce compositions with new and improved properties.

The composition preferably also comprises a plasticizer. Plasticizers include, for example, phthalate esters, polyester plasticizers, citrate esters, trimellitate esters, pentaerythritol esters, trialkyl phosphates, triaryl phosphates, aryl-alkyl phosphates, chlorinated paraffins and brominated aromatic phthalate esters do. Plasticizers can be used individually or in blends to ensure that the compositions obtained pass the thermal aging regulations (UL444) required by physical properties and all cables.

Certain plasticizers, especially triaryl phosphates, aryl-alkyl phosphates, chlorinated paraffins and brominated aromatic phthalate esters, provide flame resistance to the compositions. Thus, compositions proposed for use in plenum cables generally contain this type of plasticizer. Alkyl-aryl phosphate plasticizers include, for example, mixed phosphate esters of phenol and C ₁₂ to C ₁₆ straight chain (or branched) alcohols such that the resulting phosphate esters contain a blend of the following components: triphenyl phosphate ( i) (0 to 5%), dialkylphenyl phosphate (ii) (5 to 35%), alkyldiphenyl phosphate (iii) (65 to 95%) and trialkyl phosphate (iv) (less than 2%). Chlorinated paraffin contains 50 to 75% by weight of chlorine. Brominated aromatic phthalate esters include bis- (di-2-ethylhexyl) tetrabromophthalate. Conventional compositions typically contain about 1 to about 40 phr of plasticizers and low smoke compositions typically contain about 15 to about 40 phr of flame retardant plasticizers.

The composition may not require a flame retardant plasticizer, but may use a less expensive nonflammable plasticizer. However, if the cable needs to pass more stringent flame retardancy tests such as the UL910 test, the composition preferably comprises a flame retardant plasticizer, preferably about 8 to about 15 phr. Although higher amounts of flame retardant plasticizers can be added, preferred compositions can incorporate one or more nonflammable plasticizers to achieve the desired mechanical or aging properties at a lower cost.

The composition may also include fillers which are additives that dilute the resin without adversely affecting the mechanical properties of the composition. Fillers may also provide additional flame resistance or smoke resistance and electrical resistivity to the composition. Typical fillers are alumina trihydrate, magnesium hydroxide, magnesium carbonate, huntite, hydromagnesite and calcium carbonate.

The composition can be formulated using conventional techniques well known in the art. The components may be added individually during the compounding process or some may be formulated into a premix and added to the compounding process. In a preferred method, the resin or resins are premixed with a flame retardant and compatibilizer to form a masterbatch, which is introduced into the blending process.

The composition can be used in the manufacture of plenum cables, applications in which there is a need to enhance flame resistance and smoke resistance. This lowers costs by using smaller amounts of flame retardants to meet flame retardancy standards. It may also be formulated to be easier to use in wire and cable manufacturing processes.

Advantageous properties of the invention can be observed with reference to the following examples described, but the examples do not limit the invention.

Example

Test process

The following test process is used in the examples:

Flame and Smoke Measurements: Flame and smoke measurements are obtained with a Stanton-Redcraft conical calorimeter in accordance with ASTM 1354-94. 100 × 100 × 4 mm samples are measured in a horizontal orientation under heat reflux between 20 and 90 mm 3 / m 2. Data is recorded at 75 cc / m 2 because the fuming properties of the composition are most effectively distinguished at this heat reflux. The results are reported as follows: maximum heat release rate (PHRR, mW / m 2), cumulative emission heat (THR, MJ / m 2) at 5 and 10 minutes, highest optical density (OD _P ), specific absorption area ( Maximum velocity of specific extinction area (SEA, m 2 / kg) and cumulative specific absorption area (TSEA, m 2 -min / kg) at 5 and 10 minutes. The highest optical density represents the maximum amount of light obscuration, but the specific absorption area represents the area in the room, which is darkened per kilogram of sample.

Dynamic Thermal Stability: The dynamic thermal stability of the compositions described herein is obtained during high shear blending with a Brabender Platicorder at 50 rpm and 195 ° C. Changes in the deviations of the visible appearance or torque curves indicate degradation of the compound. The time taken to reach one of these two phenomena is recorded as the dynamic stabilization time.

Compatibility Measurements: Representative flame retardants are colored with carbon black. Samples (20 mm × 20 mm × 0.89 mm) are placed on a flat metal sheet in an air circulation oven at 100 ° C. temperature. Samples are observed daily for white effluent or chalky. Record the number of days required for any whitening of the sample to be observed.

Examples 1-5

The following composition is prepared as follows: (i) the ingredients are dry blended in a high speed mixer at room temperature, (ii) the dry blend is blended in a brabender mixer at 200 ° C. for 4 minutes, and (iii) the melt obtained The compound is pressed to the dimensions required for the conical calorimeter test.

Examples 1, 2 and 4 are comparative examples. Example 1 is a commercially available minimally fumed PVC compound. Examples 2 and 4 are compositions that are further fortified by the state of the art. Examples 4 and 5 list plenum compositions to which other important fuming inhibitors have been added. Example 5 is an embodiment of the present invention. Example 3, which does not include a compatibilizer, shows that the addition of tris (tribromoneopentyl) phosphate effectively prevents flame and smoke. However, the composition is practically not useful because the flame retardant flows out of the composition.

Examples 1-5 Ingredient (phr) ¹ Example 1 Example 2 Example 3 Example 4 Example 5 PVC 100 100 100 100 Dibasic lead phthalate (Dythal XL) 5 5 7 7 Alumina Trihydrate (ATH) - - 30 30 Huntite (Ultracarb) 55 55 - - Stearic acid One One One One Ethylene / n-butylacrylate / carbon monoxide terpolymers (Elvaloy HP441) - - - 5 Antimony oxide 3 3 - - Kemgard 911C - - 10 10 Ammonium Palmolybdate (AOM) - - 20 20 Zinc borate 2 2 - 2 Epoxidized Soybean Oil (ESO) - - 3 3 Alkyl-aryl phosphate esters (Santicizer 2148) 35 35 30 30 Brominated Aromatic Phthalates (DP-45) 20 - 20 - Tris (tribromoneopentyl) phosphate - 13 - 10 Bromine Content (wt%) 0 4.2 4.2 4.1 3.1 Conical Calorimeter Data (75㎾ / ㎡) Cumulative Heat of Release at 5 Minutes (MJ / ㎡) 29.3 25.9 14.8 28.1 27.6 Cumulative Heat of Release at 10 Minutes (MJ / ㎡) 38.8 28.4 37.6 36.9 Cumulative SEA at 5 minutes (㎡-min / kg) 4575 3568 1250 2771 323 Cumulative SEA at 10 minutes (㎡-min / kg) 19260 3817 4911 732 Heat release rate (㎾ / ㎡) 231.8 153.8 143.4 136.0 131.5 Highest optical density 0.41 0.31 0.20 0.18 0.16 The concentration of ¹ additive is expressed in parts of additive per 100 parts of vinyl halide polymer.

Examples 6-9

Examples 7 and 9, which contain tris- (tribromoneopentyl) phosphate in smaller amounts than Examples 3 and 5, are compositions of the present invention. Flame retardant properties are not significantly reduced. Examples 6 and 8 are comparative examples using reduced amounts of brominated aromatic phthalates. Flame retardant properties are significantly reduced.

Examples 6-9 Ingredient (phr) ¹ Example 6 Example 7 Example 8 Example 9 PVC 100 100 100 100 Dibasic lead phthalate (Dythal XL) 5 5 5 5 Huntite (Ultracarb) 55 55 55 55 Stearic acid One One 0.5 0.5 Antimony oxide 3 One 1.5 1.5 Zinc borate 2 2 2 2 Ammonium Palmolybdate (AOM) 12 12 20 12 Ethylene / n-butylacrylate / carbon monoxide terpolymers (Elvaloy HP441) - - 5 5 Pentaerythritol ester (Hercoflex 707A) 25 25 30 30 Alkyl-aryl phosphate esters (Santicizer 2148) 10 10 - - Trialkyl Phosphate Ester (TBEP) - - 5 5 Brominated Aromatic Phthalates (DP-45) 15 - 15 - Tris- (tribromoneopentyl) phosphate 9.6 - 7 Bromine Content (wt%) 3.0 3.0 2.9 2.2 Conical Calorimeter Data (75㎾ / ㎡) Cumulative Heat of Release at 5 Minutes (MJ / ㎡) 24.2 24.1 22.6 18.4 Cumulative Heat of Release at 10 Minutes (MJ / ㎡) - 28 30.4 24.7 Cumulative SEA at 5 minutes (㎡-min / kg) 2265 1707 1991 1711 Cumulative SEA at 10 minutes (㎡-min / kg) - 2271 2315 2101 Heat dissipation rate (kW / ㎡) 135.4 104.4 122.3 93.0 Highest optical density 0.17 0.12 0.15 0.14 The concentration of ¹ additive is expressed in parts of additive per 100 parts of vinyl halide polymer.

Examples 10 to 13

Examples 10 to 13 are compositions of the present invention. Example 10 uses nonflammable plasticizers instead of flame retardant plasticizers. Examples 11-13 show the use of fillers.

Examples 10 to 13 Ingredient (phr) ¹ Example 10 Example 11 Example 12 Example 13 PVC 100 100 100 100 Dibasic lead phthalate (Dythal XL) 5 5 5 5 Huntite (Ultracarb) 55 55 40 27.5 Calcium carbonate - - - 27.5 Stearic acid 0.5 0.5 0.5 0.5 Ethylene / n-butylacrylate / carbon monoxide terpolymers (Elvaloy HP441) - 5 5 5 Antimony oxide 3 3 3 3 Zinc borate 2 2 2 2 Ammonium Palmolybdate (AOM) 12 12 12 12 Citrate Ester (Citroflex B-6) 35 - - - Trialkyl Phosphate Ester (TBEP) - 5 5 5 Pentaerythritol ester (Hercoflex 707A) - 30 30 30 Tris- (tribromoneopentyl) phosphate 10 10 10 10 Bromine Content (wt%) 3.0 3.0 3.2 3.0 Conical Calorimeter Data (75㎾ / ㎡) Cumulative Heat of Release at 5 Minutes (MJ / ㎡) 24.7 26.9 24.3 21.3 Cumulative Heat of Release at 10 Minutes (MJ / ㎡) 27.1 39.4 32.9 28.7 Cumulative SEA at 5 minutes (㎡-min / kg) 1925 1938 2254 1615 Cumulative SEA at 10 minutes (㎡-min / kg) 2226 2791 3206 2810 Heat dissipation rate (kW / ㎡) 158.7 122.4 118.0 96.4 Highest optical density 0.15 0.17 0.16 0.15 The concentration of ¹ additive is expressed in parts of additive per 100 parts of vinyl halide polymer.

Examples 14-16

Examples 14 and 15 are comparative examples and have relatively poor dynamic thermal stability. Example 16 is a composition of the present invention, which exhibits relatively good dynamic thermal stability.

Examples 14-16 Ingredient (phr) ¹ Example 14 Example 15 Example 16 PVC 100 100 Dibasic lead phthalate (Dythal XL) 7 5 Alumina Trihydrate (ATH) 30 - Huntite (Ultracarb) - 55 Stearic acid One 0.5 Ethylene / n-butylacrylate / carbon monoxide terpolymers (Elvaloy HP441) - 5 Antimony oxide - 3 Zinc borate - 2 Barium metaborate - 6 Ammonium Palmolybdate (AOM) 30 12 Chemguard 911C 10 - Epoxidized Soybean Oil (ESO) 3 - Pentaerythritol ester (Hercoflex 707A) - 15 Alkyl-aryl phosphate esters (Santicizer 2148) 30 18 Brominated Aromatic Phthalates (DP-45) 20 - Tris (tribromoneopentyl) phosphate - 10 Bromine Content (wt%) 2.7 ^* 4.0 3.0 Dynamic thermal stability DTS (min) 4.25 13.25 30+ The concentration of ¹ additive is expressed in parts of additive per 100 parts of vinyl halide polymer. ^{* See} US Pat. No. 5,036,121. Contains additional 15% chlorine by chlorinated polyethylene in addition to chlorine provided by PVC.

Examples 17-23

These examples show the effectiveness of various compatibilizers or spill prevention agents.

Examples 17-23 Ingredient (phr) ¹ Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 PVC 100 100 100 100 100 100 100 Dibasic Lead Phthalate 5 5 5 5 5 5 5 Calcium carbonate 75.2 75.2 75.2 75.2 75.2 75.2 75.2 Stearic acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Pentaerythritol ester 20 20 20 20 20 20 20 Alkyl-aryl phosphate ester 15 15 15 15 15 15 15 Tris- (tribromoneopentyl) phosphate 10 10 10 10 10 10 10 Carbon black 3 3 3 3 3 3 3 Ethylene / n-BA / CO terpolymer ² (Elvaloy HP441) 5 Ethylene / n-BA / CO terpolymer (Elvaloy HP771) 5 Ethylene / VA / CO Terpolymer ³ (Elvaloy 741) 5 Ethylene / VA / CO terpolymer (Elvaloy 742) 5 Chlorinated Polyethylene (Tyrin 4211) 5 Ethylene Vinyl Acetate (Ultrathene UE634) 5 Compatibility data Number of days before chalkiness is first observed ⁴ One 5 4 3 8 16 8 The concentration of ¹ additive is expressed in parts of additive per 100 parts of vinyl halide polymer. ² ethylene / n-butylacrylate / carbon monoxide terpolymers. ³ ethylene / vinylacetate / carbon monoxide terpolymers. ⁴ Heated in air circulation oven at 100 ° C.

Examples 24 and 25

This example shows the stoichiometric replacement of zinc borate with boric acid and zinc oxide.

Examples 24 and 25 Ingredient (phr) ¹ Example 24 Example 25 PVC 100 100 Dibasic lead phthalate (Dythal XL) 5 5 Huntite (Ultracarb) 55 55 Stearic acid One One Antimony oxide One One Zinc borate 2 - Zinc oxide 0.8 Boric acid 1.2 Ammonium Palmolybdate (AOM) 12 12 Ethylene / n-butylacrylate / carbon monoxide terpolymers (Elvaloy 441) - - Pentaerythritol ester (Hercoflex 707A) 30 30 Alkyl-aryl phosphate esters (Santicizer 2148) - - Trialkyl Phosphate Ester (TBEP) 5 5 Brominated Aromatic Phthalates (DP-45) - - Tris- (tribromoneopentyl) phosphate 9.6 9.6 Bromine Content (wt%) 3.0 3.0 Conical Calorimeter Data (75㎾ / ㎡) Cumulative Heat of Release at 5 Minutes (MJ / ㎡) n / a n / a Cumulative Heat of Release at 10 Minutes (MJ / ㎡) n / a n / a Cumulative SEA at 5 minutes (㎡-min / kg) n / a n / a Cumulative SEA at 10 minutes (㎡-min / kg) n / a n / a Heat dissipation rate (kW / ㎡) 124.8 127.0 Highest optical density 0.17 0.17 The concentration of ¹ additive is expressed in parts of additive per 100 parts of vinyl halide polymer.

Example 26

The composition of Example 7 was mixed in a high speed Henschel mixer, extruded into pellets and coated with 24 gauge copper conductor at an average wall thickness of 0.20 mm. Cut the insulated wire and twist it in 4 pairs. The twisted conductors are coated with the composition in a 0.63 mm thick semi-pressure packed jacket. The cable obtained is evaluated by the UL 910 test protocol.

Large scale UL 910 rating Test parameters Example 26 Exam details Highest optical density 0.25 0.50 max Average optical density 0.14 0.15 max Flame Spread (ft) 1.5 Up to 5

Having described the present invention, the inventors now claim the following and their equivalents.

Claims (41)

Poly (vinyl chloride) resin, chlorinated poly (vinyl chloride) resin or mixtures thereof (a), At least one flame retardant (b) A flame retardant low smoke composition comprising a compatibilizer (c). Formula I In Formula I above, M is sulfur or oxygen, X ¹ , X ² and X ³ are each independently halogen selected from the group consisting of chlorine and bromine. The composition of claim 1 wherein M is oxygen. The composition of claim 2 wherein X ¹ , X ² and X ³ are each bromine. The composition of claim 3 comprising about 2 to about 20 phr of a flame retardant. The composition of claim 4 wherein the weight ratio of the compatibilizer to the flame retardant is in the range 0.1: 1.0 to 2.0: 1.0. The composition of claim 5, wherein the compatibilizer delays chalking of the composition for at least 3 days during accelerated aging. The composition of claim 6 wherein the resin is poly (vinyl chloride). The composition of claim 1, wherein the compatibilizer delays chalking of the composition for at least 3 days during accelerated aging. The composition of claim 8, wherein X ¹ , X ² and X ³ are each bromine and M is oxygen. 10. The composition of claim 9 wherein the compatibilizer is selected from the group consisting of copolymers of ethylene and vinyl acetate, terpolymers of ethylene, vinyl acetate and carbon monoxide, chlorinated polyethylene, vinyl chloride / ethylene copolymers and thermoplastic polyurethanes. The composition of claim 1 wherein the compatibilizer is selected from the group consisting of copolymers of ethylene and vinyl acetate, terpolymers of ethylene, vinyl acetate and carbon monoxide, chlorinated polyethylene, vinyl chloride / ethylene copolymers and thermoplastic polyurethanes. 12. The composition of claim 11, wherein X ¹ , X ² and X ³ are each bromine and M is oxygen. The composition of claim 12 wherein the compatibilizer is a terpolymer of ethylene, vinyl acetate or n-butyl acrylate and carbon monoxide. The composition of claim 13 comprising from about 2 to about 20 phr of a flame retardant, wherein the weight ratio of the compatibilizer to the weight ratio of the flame retardant is from 0.1: 1.0 to 2.0: 1.0. 15. The flame retardant and other halogenating additive of claim 14, wherein the halogen content is sufficient to provide a composition that is about 2.0 to about 7.0 weight percent more than the halogen content of the poly (vinyl chloride) resin, chlorinated poly (vinyl chloride) resin, or mixtures thereof. A composition containing a. The composition of claim 1 further comprising boron oxide or a boron containing salt. The composition of claim 1, further comprising a boron-containing compound selected from the group consisting of zinc borate, calcium metaborate, barium metaborate, calcium pyroborate, potassium tetraborate, boron oxide, boric acid, and ammonium pentaborate. 18. The composition of claim 17, wherein X ¹ , X ² and X ³ are each bromine and M is oxygen. 19. The composition of claim 18, comprising from about 2 to about 20 phr of a flame retardant, wherein the weight ratio of the compatibilizer to the weight ratio of the flame retardant is from 0.1: 1.0 to 2.0: 1.0. The composition of claim 19 wherein the compatibilizer is selected from the group consisting of copolymers of ethylene and vinyl acetate, terpolymers of ethylene, vinyl acetate and carbon monoxide, chlorinated polyethylene, vinyl chloride / ethylene copolymers and thermoplastic polyurethanes. The composition of claim 20 wherein the boron oxide or boron-containing salt is selected from the group consisting of zinc borate, calcium metaborate, barium metaborate, calcium pyroborate, potassium tetraborate, boron oxide, boric acid and ammonium pentaborate. The flame retardant and other halogenation additive of claim 21 wherein the halogen content is sufficient to provide a composition that is about 2.0 to about 7.0 wt% more than the halogen content of the poly (vinyl chloride) resin, chlorinated poly (vinyl chloride) resin, or mixtures thereof. A composition containing a. 23. The composition of claim 22, wherein the boron oxide or boron containing salt is zinc borate. The composition of claim 1 comprising about 8 to about 15 phr smoke inhibitor. The composition of claim 24 wherein the fuming inhibitor is ammonium palmybdate. The composition of claim 1 which does not comprise a fuming inhibitor. The composition of claim 1 comprising 1 to 40 phr of a plasticizer. The composition of claim 27 comprising 5 to 18 phr of flame retardant plasticizer. The composition of claim 28 wherein the plasticizer is an alkyl aryl phosphate ester. The composition of claim 1 further comprising a filler. The composition of claim 30 comprising about 20 to about 70 phr of filler. 32. The composition of claim 31 wherein the filler is selected from the group consisting of alumina trihydrate, magnesium hydroxide, magnesium carbonate, huntite, hydromagnesite and calcium carbonate. The composition of claim 1 which passes the UL 910 test. 34. The composition of claim 33 wherein M is oxygen, X ¹ , X ² and X ³ are each bromine and comprise from about 2 to about 20 phr of a flame retardant and the weight ratio of the compatibilizer to the weight ratio of the flame retardant is from 0.1: 1.0 to 2.0. The composition is: 1.0. 35. The composition of claim 34, wherein the compatibilizer delays chalking of the composition for at least 3 days during accelerated aging. 35. The composition of claim 34, wherein the compatibilizer is selected from the group consisting of copolymers of ethylene and vinyl acetate, terpolymers of ethylene, vinyl acetate and carbon monoxide, chlorinated polyethylene, vinyl chloride / ethylene copolymers and thermoplastic polyurethanes. 37. The composition of claim 36, comprising about 8 to about 15 phr of ammonium palm molybdate. 37. The composition of claim 36, wherein the resin is poly (vinyl chloride). 37. The flame retardant and other halogenating additive of claim 36, wherein the halogen content is sufficient to provide a composition that is about 2.7 to about 4.0 weight percent more than the halogen content of the poly (vinyl chloride) resin, chlorinated poly (vinyl chloride) resin, or mixtures thereof. A composition containing a. The compatibilizer of claim 33 wherein the compatibilizer is a terpolymer of ethylene, vinyl acetate or n-butyl acrylate and carbon monoxide, comprising from about 2 to about 20 phr of a flame retardant, wherein the weight ratio of the compatibilizer to the weight ratio of the flame retardant is 0.1: The composition is from 1.0 to 2.0: 1.0. 41. The composition of claim 40, wherein the resin is poly (vinyl chloride).