DE2725737A1 - LOW SMOKE PLASTICIZED POLYVINYL HALOGENIDE MATERIALS - Google Patents

Description

TlEDTKE - BüHLING - KlNNE -

· ■ 3-

Patent attorneys:

Dipl.-Ing. Tiedtke Dipl.-Chem. Bühling Dipl.-Ing. Kinne Dipl.-Ing. Group

Bavariaring 4, P.O. Box 20 24 8000 Munich 2

Tel .: (0 89) 53 96 53-56

Telex: 5 24 845 tipat

cable. Germaniapatent Munich

June 7, 1977

B 8227 / case F-5056 KDN1

UNIROYAL, Inc. New York, N.Y. 10020 / USA

Low-smoke plasticized polyvinylhalogenate -: ri.i i'-r.

809835/0471

Dresdner Bank (Munich) Account 3939 844 Postal check (Munich) account 670-43-8O4

B 8227

_ 4 _ ₍ 2726737

The invention relates to low-smoke or smoke-retardant plasticized polyvinyl halide polymer materials which contain 2 to 30 parts of zinc oxide as a smoke-retardant agent.
5

Zinc oxide was used together with polyvinyl chloride as a stabilizer (US-P3 3,446,765), as a pigment (US-PS 2,632,484) and used as a stabilizer for blowing agent promoters (U.S. Patent 3,041,193).

Synthetic materials that are forced to burn emit smoke and toxic gases that conjure up critical fire hazards, as they hinder or prevent escape, cause damage, restrict survival and hinder fire fighting. The latest statistics say that around half of the deaths or accidents in fires were more likely to be caused by smoke, than by heat or the actual fire, what the need to develop synthetic organic Makes understandable or emphasizes materials with the least possible smoke development. This is particularly true for such applications as linings for aircraft, ships, motor vehicles and building interiors as well as for furniture or facilities and the like.

When violently burned, polyvinyl halide materials will emit known large amounts of black smoke and materials that contain plasticizers such as dioctyl phthalate contain even more smoke than non-plasticized analog masses. Flame retardants such as oxides of tin, lead, magnesium, manganese, tellurium, titanium, copper, chromium, aluminum, vanadium and tungsten are used as smoke retardants in polyvinyl halides worthless. In fact, antimony oxide can do that on wider

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■ · ORIGINAL INSPECTED

13 iil

5 ²⁷ 25 '37 ^r

As i ^r lammverzögerer in Polyvinylhalogenidmassen applied v base; ird, often reinforce the smoke during forced combustion.

According to one aspect of the invention there is therefore a plasticized polyvinyl halide with 2 to 30 parts by weight Zinc oxide provided. According to a further aspect, the invention relates to a mixture of plasticizers, an antimony compound as a flame retardant and 2 to 30 parts by weight of zinc oxide compounded polyvinyl halide. The preferred blend of plasticizers is a blend of an alkyl trimellitate and one Alkyl phthalate with antimony trioxide as the preferred antimony compound. Still another aspect concerns

15 the incorporation of calcium carbonate or magnesium oxide as synergistic fillers.

According to the invention, materials with a markedly reduced tendency to smoke when burning, i. E. a highly desirable property in terms of safety, and the invention thus leads to one Improvement of the safety characteristics of construction materials.

In practicing the invention, 2 to 30 parts of zinc oxide are used as a smoke retardant Agent used in a calibrated polyvinyl halide. On polyvinyl halide resins which can be used in the context of the invention include homopolymers, copolymers and poly-

30 mixes. Exemplary for applicable polyvinyl halide resins are:

1. Homopolymers such as polyvinyl chloride, polyvinyl bromide,

Polyvinyl fluoride, polyvinylidene chloride, polydi-35 chlorostyrene and the like;

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2. Copolymers such as ζ.P. of vinyl chloride-vinyl acetate, Vinyl chloride-vinyl alcohol, vinylidene chloride-vinyl chloride, Yinyl chloride diethyl maleate, vinyl chloride esters of unsaturated alcohols and unsaturated ones Acids and the like; and

3. Mixtures such as polyvinyl chloride and polydichlorostyrene; Polyvinyl chloride and vinyl acetate-vinyl chloride copolymer; and polyvinyl chloride, polyvinylidene chloride and a copolymer of vinyl chloride and diethyl maleate and the like.

The resins can be treated with the zinc oxide smoke retardant in any suitable manner. In In some cases the smoke delay can be achieved by treating one or more surfaces of a plastic object can be achieved with the additive-containing resin composition, so that a treated surface with the additional mass is coated, i.e. superimposed or "padded". Similarly, textile materials of all types and constructions or construction materials with a layer or thin skin of the additional mass are superimposed.

Suitable plasticizers for the above types of resins, especially for polyvinyl chloride, are generally used in the range of 30 to 100 parts by weight per 100 parts by weight of polyvinyl halide, and they include high boiling points Esters such as bis [2-ethylhexyl adipate, bis [2-ethylhexyl azelate, Diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tri-n-butyl citrate, acetyl tri-n-butyl citrate, epoxidized soybean oil, 2-ethylhexylepoxytallate, Diethylene glycol dipelargonate, methylphthalyl ethyl glycolate, Butyl phthalyl butyl glycolate,

Bis [2-ethylhexyl] isophthalate, butyl oleate, tris [2-

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ethylhexyl phosphate, tributoxyethyl phosphate, cresyl diphenyl phosphate, Tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Butyloctyl phthalate, üi-n-octyl phthalate, Diisooctyl phthalate, bis- | 2-ethylhexyl phthalate, n-octyl-n-decyl phthalate, isooctyl isodecyl phthalate, Diisodecyl phthalate, ditridecyl phthalate, diphenyl phthalate, isodecyl benzyl phthalate, adipic acid polyester (MW 2200), azelaic acid polyester (MW 1500), sebacic acid polyester (MW 800), methyl ricinoleate, n-butyl acetyl ricinoleate, Bis-I2-ethylhexyl-sebacate, butyl-acetoxystearate, Alkyl sulfonic acid esters of phenol and cresol and tris (2-ethylhexyl) trimellitate.

Other suitable plasticizers include chlorinated (54 % chlorine) diphenyl, hydrogenated terphenyls, polyalkynaphthalenes, chlorinated (24-70% chlorine) paraffin, H-cyclohexyl-p-toluenesulfonamide, and copolymers of a conjugated diolefin having fewer than 7 carbon atoms such as butadiene with a copolymerizable monomer such as acrylonitrile or methyl isopropenyl ketone.

A particularly effective plasticizer has been found to be used for minimal smoke development a mixture of a phthalate type plasticizer and a trimellitate plasticizer is formed. A mixture or a blend of these two plasticizers in a weight ratio of phthalate to trimellitate of about 6/1 to about 1/1 gives a synergistic interaction when combined with zinc oxide smoke retardant and antimony trioxide flame retardant.

In general, compositions according to the invention with improved flame retardancy by incorporation of Metal compounds are obtained in an amount of about 1 to 30 wt / o of said polymer mass

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which the metal is formed by antimony, arsenic, or bismuth will. Antimony oxide is the preferred compound for use within the scope of the invention, however many other antimony compounds are also suitable. Suitable antimony compounds include the sulphides of antimony, Salts of alkali metals of Group I of the periodic table, antimony salts of organic acids and their pentavalent derivatives and the esters of antimonic acids and their pentavalent derivatives. It is appropriate Use sodium or potassium antimonite when applying an alkali metal salt of antimony for that materials according to the invention is desired. In US-FS 2,996,528 suitable antimony salts of organic grounds Acids and their pentavalent derivatives are given.

Compounds of this class include antimony butyrate, antimony valerate, antimony caproate, antimony heptylate, antimony caprylate, antimony pelargonate, antimony caprate, antimony cinnamate, antimony anisate and their pentavalent dihalide derivatives. The esters of antimony acids and their pentavalent derivatives are also given in US Pat . beta-chloro-ethyl) -antimonite, tris (beta-chloro-propyl) -antiraonite, tri (beta-chloro-butyl) antimonite and their pentavalent dihalide derivatives. Koch's other suitable organic antimony compounds are the cyclic antimonites such as trimethylolpropane antimonite, pentaerythritol antimonite and glycerol antimonite. The corresponding arsenic and bismuth compounds can also be used, in particular the oxides of arsenic and bismuth.

Other compounding ingredients can be used in the polyvinyl halide materials of the invention are including light and heat stabilizers, waxes, pigments, blowing agents or blowing agents, other flame retardant agents and fillers such as carbon black, silica, barytes, clay, wood flour, magnesium oxide,

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~ y ~ ι

Calcium carbonate and the like. When magnesium oxide or calcium carbonate are used as fillers, a synergistic reduction in smoke development occurs.
5

The prior art states that there is usually a direct relationship between the smoke delay achievable and the amount of smoke retardant applied, and usually a larger amount Smoke retarder a greater degree of smoke retardation is achieved with otherwise the same factors. In In some cases there is a practical upper limit on the amount of smoke retardant applied. These The upper limit is determined by secondary factors such as costs, ease of mixing or disruption with respect to some other desirable properties of the substrate. In the particular case of the present Invention was surprisingly found that the expected direct relationship between smoke delay and smoke retardant quantity does not prevail. In the case of zinc oxide plus a mixture of one Phthalate plasticizer and a trimellitate plasticizer for a total plasticizer content of about 70 parts per 100 parts (phr) the smoke development decreases rapidly when the amount of zinc oxide is up to about 7 parts per 100 parts Polyvinyl chloride increases and then the smoke generation surprisingly increases when the amount of zinc oxide increases from about 10 parts to 30 parts per 100 parts of polyvinyl chloride. When the plasticizer content increases, the optimal zinc oxide concentration also increases. That is, the preferred amount of zinc oxide is around 3 to 30 parts per 100 parts of polyvinyl halide and the most preferred amount for minimal smoke generation is 2 to 10 parts per 100 parts of polyvinyl halide when the plasticizer content is 30 to 50 parts and 5 to 12 parts when the plasticizer content is 50 to 100 parts.

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The preparations according to the invention can be used in any applications where plasticized Polyvinyl halides are acceptable including (but not limited to) coated fabrics, wires and cable iso-5 linings and jackets, wall coverings and the like. Examples of suitable fibrous Base materials for fabric coatings are cotton fabrics, rayon fabrics, felt, paper, polyester fabrics and mixtures of the foregoing. The fabrics can be 10 by calendering, by cast coating, by "PIastisol" coating, can be coated by roll coating or other methods known to those skilled in the art are.

In practicing the invention, the zinc oxide smoke retardant, the antimony compound flame retardant, the fillers and other compounding G ingredients into the resin by any suitable mixing technology available to the person skilled in the art can be mixed in.

In the examples given below, all compositions or materials were prepared as follows, Unless otherwise stated: The components were

the first mixed by hand and then for 10 minutes which was maintained at 150 ⁰ C in an electrically heated two-roll mill differential. The homogeneous mixture was then in a hydraulic 30 ton press for 10 minutes at 160 ° C under full pressure in a

30 7.62 χ 15.2 cm 0.51 mm form compression molded. For testing The smoke development of the various materials made test specimens 7.62 7.62 cm about 0.56 mm the compositions made to flow by compression molding, plate produced as indicated above

cut out. The individual test specimens were on

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Aluminum foils arranged on top of the overlap the surface of the fibrous body on all four sides were cut to allow size. The wrapped specimens were placed in a holder and in an Aminco NBS smoke chamber according to the specifications of the NBS Technical Note 708 burned down from December 1971. The amount of smoke was measured with a photomultiplier. The specific optical Density was determined and then corrected for the soot remaining on the lenses at the end of the test. The attenuation of a light beam as a result of smoke accumulation in a closed chamber was measured the flame combustion. The results are expressed in terms of specific optical density values that is obtained via a geometry factor and the measured optical density (extinction). This is the one for that "Smoke concentration" is the most characteristic single measurement. The photometric scale for smoke measurement according to this The test method is similar to the brightness scale or optical density scale for human eyesight.

Materials with no zinc oxide present give a corrected maximum specific optical density in the range of 400 or more. In comparison, 10 parts of zinc oxide reduce this number to less than about 200 degraded. In the NBS test, the lower numerical value corresponds to lower smoke development. It's closed note that most fourths averages the maximum specific optical density of a material of Measurements on two or more test pieces per material are. In general, two materials tend to be different considered in terms of smoke development properties when the difference in the maximum specific optical densities is greater than 10.

More details about reducing smoke

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development are shown in the following examples, in which all compositions in parts by weight are given per 100 parts of polyvinyl chloride resin. All compositions contained 1.8 parts of a barium-cadmium-zinc stabilizer, 2.7 parts epoxidized soybean oil and 0.2 parts stearic acid unless otherwise is specified.

10 Example 1

A composition comprising 100 parts of polyvinyl chloride (Marvinol® S / 22 from Uniroyal, Inc.), 70 parts by weight Dioctyl phthalate plasticizer (DOP), 15 parts by weight CaI

15 parts by weight of cium carbonate filler, 10 parts by weight of antimony trioxide (SbpO ₇ ) and 10 parts by weight of zinc oxide were mixed by hand and then rolled on a two-roll mill for 10 minutes. The composition was as previously described to a thickness of about 0.56 mm

compression molded. Two samples, each 7.62 cm square, were then cut from the plate and placed in relation to the Smoke development in the Aminco MBS smoke chamber tested using the flame test.

The above procedure was then repeated except that the zinc oxide was omitted.

The following mean maximum specific optical densities were found for the two compositions obtain:

with zinc oxide 176

without zinc oxide

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- 13 - ι Example 2

The procedure of Example 1 was repeated using different plasticizers. the The compositions and smoke development results are summarized in Table I below.

The names given in the table for the plasticizers correspond to the following composition: 10

Fhthalate type

Santicizer 711 = mixed (C ₇ -C ₁₁ ) alkyl

phthalate '' '

PX-316 = mixed alkyl phthalate with

15 higher linear percentage

than with the Santicizer 711

Phosphate type

Santicizer 141 = 2-ethylhexyl-diphenyl-phosphate Santicizer 148 = isodecyl diphenyl phosphate

Trimellitate type

Santicizer 79TH = mixed (C _v -C _q ) alkyl trimellitate '*

The results of Table I clearly show that the incorporation of 10 parts by weight of zinc oxide leads to a drastic increase in weight See reduction in the amount of smoke produced by the compositions that use antimony trioxide as a flame retardant Contains agents, regardless of the plasticizer present.

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composition Table 1

co

OB cn

Polyvinyl chloride zinc oxide Santicizer PX-31 β

Santicizer Santicizer Santicizer 79TM Calcium Carbonate Antimony trioxide

maximum specific optical density

100 10C 100 100 100 100 100 0 10 10 10 10 • 1C 10 60 70 6ο 60

60

60

15th 15th 15th 15th 15th 80 30th 10 10 10 10 10 15th 10 10

373 161 160 16Ο 162 162 157

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- 15 Example 3

The procedure of Example 2 was repeated using different fillers to demonstrate that zinc oxide in spite of different absolute amounts of development in special compositions acts as a smoke retardant in all cases, depending on the filler and the amount of filler. Maximum smoke suppression was obtained when calcium carbonate was used as the filler. The compositions and results are shown in Table II below.

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Table II Assemble long

Polyvinyl chloride 09 zinc oxide 09835 Magnesium oxide
Calcium carbonate "Ν.
O Santicizer 711 DOP Antimony trioxide

maximum specific optical density

160

100 100 100 100 100

0 10 10 10 10 10

30 15 15 20 30 60 60 60

70 70 70

10 10 10 10 10 10

163 176 185 172

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Example 4

The procedure of Example 1 was repeated to determine the effect of an addition of antimony trioxide (Sb ₉ O ,,) on smoke generation from polyvinyl chloride compositions. With the mixed alkyl phthalate calibrant (PX-316) given in Example 2 and the filler combination used in these compositions, a synergistic effect between zinc oxide and antimony trioxide in terms of smoke suppression was achieved.

The compositions and results are given in Table III.

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Table III

CD OD C *>

Composition N *

Polyvinyl chloride 100 100 100 zinc oxide 10 10 0 PX-516 60 60 60 Calcium carbonate 15th 15th 15th Antimony trioxide 0 10 10 maximum specific
optical density 225 160 549

* a tin stabilizer ("Thermolite 51" - an organotin mercaptide

from M & T Chemicals Corp.), 2phr, was used in place of the epoxidized ^ ^te

Soybean oil and Ba / Cd / Zn stabilizer are used. ^ ro

Ii c3227

example 5

The procedure of Example 1 was repeated to show the relationship between zinc oxide concentration and smoke suppression. It should be noted that the effect of zinc oxide on the reduction
smoke development is complex and at the beginning shows a decrease in smoke development as the amount of zinc oxide increases, after which - quite surprisingly - an increase

would take the smoke development above an optimal amount
from about 5 to 12 parts by weight per 100 parts by weight of polyvinyl chloride for a compounding with 70 parts (per
100 parts) plasticizer is recorded. The compositions and results are shown in Table IV below

15 reproduced.

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Table IV composition

Polyvinyl Chloride Zinc Oxide Santicizer Santicizer 79TM Calcium Carbonate Antimony trioxide

maximum specific optical density

100 100 100 100 100 100 100 0 1 3 5 10 20th 30th 50 50 50 50 50 5C 50 20th 20th 20th 20th 20th 20th 20th 15th 15th 15th 15th 15th 15th 15th 10 10 10 10 10 10 10

226

251

163

156

170

192

CC (V!

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Example 6

This example shows that numerous other zinc compounds can be used either as smoke retardants for polyvinyl chloride materials ineffective or decidedly less effective than zinc oxide.

Test panels were made according to the procedure of Example 1 from the following basic composition:

Polyvinyl chloride 100 Santicizer 711 50 Santicizer 79TM 20th Calcium carbonate 15th Of timon trioxide 10 Zinc compound 10

The following results were obtained for the various zinc compounds:

link maximum specific opti
cal density X zinc oxide 156 Y Zinc sulfate 2 ^ 1 Z Zinc sulfide 318 AA Zinc borate 207 A3 Zinc nitrate 203 AC without 321

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Example 7

The procedure of Example 1 has been used to illustrate the synergistic effect of a mixture of a phthalate type plasticizer and a trimellitate plasticizer on the smoke development in preparations with an optimal amount of zinc oxide as a smoke retarder and antimony trioxide repeatedly as a flame retardant agent. The synergistic effect is with a weight ratio of phthalate plasticizer to trimellitate plasticizer from about 6/1 to about 1/1 can be observed.

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Table V composition

ο polyvinyl chloride

0 ° zinc oxide

"Santicizer 711

S Santicizer 79TM

- * calcium carbonate Antimony trioxide AD AE Aj ^ AG

1OC 100 100 100 100 10 10 10 10 10 70 60 50 33 0 0 10 20th 33 80 15th 15th 15th VJl 15th 10 10 10 10 10

maximum specific optical density ^{161 1} ^ ^ 6 145 137

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-Zh-

Example 8

Coated fabrics were prepared by mixing a coating compound on a two-roll roller-5 factory as in example 1 and subsequent calendering the compounding on a polyester-cotton knit

fabric of 84.7 g / m 2 produced according to standard techniques] A coating thickness of 0.305 mm was obtained with a

84.7 g / m fabric made using standard techniques.

5di temperature of 150 C provided.

The following compositions were applied to the polyester cotton fabric to give the the following smoke values:

15 AI AJ * AK

Polyvinylchloride 100 100 100 Santicizer 711 50 50 60 Santicizer 79TM 20th 20th 0 Calcium carbonate 15th 15th 15th Antimony oxide 10 10 10 zinc oxide 0 10 10 maximum specific optical density 165 89 122

* Thermolite 31 (2phr) was used in place of the Ba / Cd / Zn stabilizer is used.

Example 9

This example shows that the optimal amount of zinc oxide, such as it is shown in Example 5 increases when the amount of plasticizer in a plasticized poly-

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vinylchloridmacse is increased. The results are in Table VI below.

Table VI

Total amount of plasticizer optimal ZnO concentration (phr) (phr)

20 0.5

30 about 40 5

50 about

70 10-12

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Claims (8)

Claims 30 to 100 parts by weight per 100 parts by weight of polyvinyl halide, characterized by the presence an amount of zinc oxide of 2 to 30 parts by weight which reduces smoke when burning. 10 2. Material according to claim 1, characterized in that the polyvinyl halide by polyvinyl chloride and its copolymers is formed. 3. Material according to claim 1, characterized in that that the plasticizer in an amount of about 30 to 50 parts by weight per 100 parts by weight of polyvinyl halide and the zinc oxide is present in an amount of about 2 to 10 parts by weight. 4. Material according to claim 1, characterized by a plasticizer content of about 50 to 100 parts by weight per 100 parts by weight of polyvinyl halide and a zinc oxide content of about 5 to 12 parts by weight. 5. Material according to claim 1, characterized in that the plasticizer from the group of phthalates, phosphates, Trimellitate and mixtures thereof is selected. 6. Material according to claim 1, characterized by an additional content of up to about 30 parts by weight of antimony oxide (SbpO,). 7. Material according to claim 1, characterized by a 809835/0471 ^r 'original inspected B 8227 - Z> - ι • a · additional content of up to about 60 parts by weight of filler from the calcium carbonate and magnesium oxide educated group. 8. Material according to claim 1, characterized in that that the plasticizer by a mixture of dialkylphtha- lat and alkyl trimellitate is formed. 809835/0471