Low smoke plasticized polyvinyl chloride

PATENT DESCRIPTION

Additional patent to pilgrim No. -Pending: 06.12.76 (P. 194194)

Priority: 08/12/75 United States of America

The application was announced: 26.09.77

Patent description published: 15.11.1979

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Inventor: Patent holder: Uniroyal Inc., New York (United States of America)

A mixture of plasticized polyvinyl halide that produces little smoke and smoke when burning

The subject of the invention is a mixture of plasticized polyvinyl halide producing little dyne during smoking #.

U.S. Patent 3,446765 discloses a blend of non-plasticized polyvinyl chloride containing finely divided calcium carbonate, which discoloration after light prevents the addition of less alkaline earth metal oxides or hydroxides.

This mix consists of parts by weight of 100 PVC, 10 CaCO $ coated with stearin H, barium-cadmium stabilizer, 3.5 fatty acid ester lubricant, and 0.5 titanium oxide, which can be replaced by zinc oxide.

U.S. Patent No. 2,682,464 describes a blend of plasticized polyvinyl chloride for coating medical materials that is waterproof, suitable for sterilization and cleaning. This mix includes 20.80 * / · powdered polyvinyl chloride, 14.50 * / polypropylene glycol adepate, 40.80% pigment, 3.60 · ethyl acetate, 3.70% ethyl alcohol and 2.20 * / · Isopropyl alcohol, however, this pigment may contain up to 12.1 * / · zinc oxide.

U.S. Patent No. 3,041,191 relates to a method for producing a laminated, plasticized sheet comprising, inter alia, as an upper cellular layer - a polyvinyl chloride blend. The top layer of the plasticized sheet is made of a mixture comprising 100 parts by weight of polyvinyl resin, 113 parts by weight of plasticizer, 5 parts by weight of blowing agent and other additives in an amount of e.g. 2.5 parts by weight of zinc oxide and 2-20 parts by weight of pigment, and synthetic materials exposed to forced burning emit smoke and toxic gases, which is dangerous in the event of a fire * because it makes it difficult to escape, causes injury, reduces retention life and interferes with attempting to fight the fire. Recent statistics have shown that about half of the woes associated with fire accidents are caused by the effect of smoke rather than heat or actual burning. Therefore, there is a need to develop synthetic organic materials with the lowest smoke production properties possible. This is especially true for applications such as lining in aircraft, watercrafts, motor vehicles, home interiors, furniture and the like.

It is known that during forced burning of polyvinyl halide mixtures, large amounts of black smoke are evolved, with mixtures which contain plasticizers such as

103 507

103 567 octyl phthalate, give off even more smoke than their non-plasticized counterparts.

Flame retardants such as tin, lead, magnesium, manganese, tellurium, titanium, copper, chromium, aluminum, vanadium and tungsten oxides are worthless as anti-smoke agents in a mixture with polyvinyl halide. Moreover, antimony oxide, which is widely used as Wednesday ^:. inhibitory / flame in mixtures with polyvinyl halide during forced smoking, can often increase smoke production.

The present invention relates to a blend of plasticized polyvinyl halide with a suitable amount of zinc oxide as a means of suppressing smoke production. According to the invention, polyvinyl halide is combined with a mixture of plasticizers, an antimony compound as a flame retardant, one or more fillers and a suitable amount of zinc oxide as a means of inhibiting the production of smoke. A preferred mixture of plasticizers is a blend of alkyl trimelitate and alkyl phthalate with antimony trioxide as the preferred antimony compound. The preferred filler is calcium carbonate.

Thus, the invention serves to obtain mixtures with a significantly reduced tendency to smoke during burning, a very desirable safety property. Accordingly, the invention provides an improvement in the safety features of the materials used in the constructions.

In the practice of the invention, zinc oxide, as an anti-smoke agent, is used to obtain plasticized polyvinyl halide that produces low smoke when smoking.

Polyvinyl halide resins useful in this invention include homopolymers, copolymers and mixtures of polymers. Examples of such resins are:

1. Homopolymers such as polyvinyl chloride, polyvinylbromide, polyvinylfluoride, polyvinylidene chloride, polydihydrogen chloride, etc.

2. Copolymers such as vinyl chloride - vinyl acetate, vinyl chloride - vinyl alcohol, vinylidene chloride - vinyl chloride, vinyl chloride - ethyl maleate, vinyl chloride - chlorinated esters of unsaturated alcohols and unsaturated acids etc. and

3. Mixtures such as polyvinyl chloride and polydichloro &amp; tyrene, polyvinyl chloride and vinyl acetate-vinyl chloride copolymer, and polyvinyl chloride, polyvinylidene chloride and vinyl chloride-ethyl maleate copolymer, and the like.

Resins can be treated with anti-smoking additives in any known way. In some cases, smoke suppression can be achieved by covering one or more surfaces of the plastic object with a smoke suppressing compound, e.g., by applying a layer or by surfacing. In a similar way, any type of textiles and constructions can be coated with a layer or thin cover of a smoke-suppressing mixture.

Suitable plasticizers for the resins included in the blend, especially for the polyvinyl chloride itself, are plasticizers usually used in an amount of 20-100 parts by weight per 100 parts by weight polyvinyl halide, preferably 30-100 parts, high-boiling esters such as: di (2-ethylhexyl) adipate, di (2-ethylhexyl) azelate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tri-n-butyl citrate, tri-n-butyl acetyl citrate, epoxidized soybean oil, 2-ethoxylate epoxylate diethylene glycol, methylphthalate ethyl glycolate, butylphthalate butyl glycolate, di (2-ethylhexyl) isophthalate, butyl oleate, tri (2) ethylhexyl phosphate), tri-butoxyethyl phosphate, cresyl diphenyl phosphate, Tricresyl phosphate, 2-ethylhexyl diphenylphosphate, butyl octylphthalate, di-octyl phthalate, diisoctyl phthalate, di (2-ethylhexyl) phthalate, n-decyl n-decylphthalate, dioctylphthalate phthalate, phthalene phthalate, isodicyl, polyester adipic acid (molecular weight 6000), polyester adipic acid (molecular weight 2200), polyester aiselaic acid (molecular weight 1500), polyester of sebacic acid (molecular weight 800), methyl ricinolate, n-butyl acetylorycinolate, di (2-ethylhexyl) sebacate, butyl acitoxystearate, alkylsulfonic acid phenyl and cresyl ester and tri (2-ethylhexyl) tri-citrate.

Other suitable plasticizers are: chlorinated (54% chlorine) diphenyl, hydrogenated 1,4-diphenylbenizens, polyalkylnaphthalenes, chlorinated (24-70% chlorine) paraffin, N-cyclohexylamide of p-toluenesulfonic acid and conjugated diolefins with less than 7 carbon atoms, as butadiene, with a copolymerizable monomer such as acrylonitrile or ketone, methyl isopropenes.

It has been found that a mixture of phthalate-type plasticizer with tripellite plasticizer is a particularly effective plasticizer to achieve minimal smoke formation. A mixture of two plasticizers in a weight ratio of phthalate to trimelite from about 6: 1 to about 1: 1 causes synergy in mutual interaction when combined with zinc oxide as an anti-smoke agent and antimony trioxide as a flame suppressant.

Typically, improved flame suppression of the inventive blends can be achieved by incorporating metallic compounds in which the metal is antimony, arsenic or bismuth in an amount of about 1 to 30% by weight of the polymer blend. Antimony oxide is preferably used, although many other antimony compounds may also be used. Suitable antimony compounds are: antimony sulfides, alkali metal antimony salts of the 1st group of the periodic table, organic antimony salts and their pentavalent derivatives as well as antimony acid esters and their pentavalent derivatives. As the alkali metal salt of antimony, the composition of the invention preferably contains sodium or potassium antimonate.

In United States Patent A103 567 of US Pat. No. 2,996,528, the corresponding salts of organic acid antimony are given for their polyquivalent derivatives. Compounds from this group include: antimony butyrate, antimony valerate, antimony capronate, antimony enanthate, antimony caprylate, antimony pela tgonate, antimony caprate, antimony cinnamate, antimony p-metofesybenzoate and their pentahydric divalent derivatives.

Also, U.S. Patent No. 2,993,924 provides esters of antimony acids, such as tri-n-octyl antimonin, tri (2-ethylhexyl) antimonin, tri-benzyl antimonin, tri - / - chloro (meityl) antimonin. , tri - / ^ - chloropropyl antimonin /, tri - //? - chlorobutyl antimony / and their pentavalent dihalide derivatives. Still other suitable organic antimony compounds are cyclic antimonlins such as trimethylpropane antimony, pentaerytribium antimony and glycerin antimony. Appropriate arsenic and bismuth compounds may also be used, especially arsenic and bismuth oxides.

Other ingredients that may be included in the polyvinyl halide blends of the Invention include light and heat resistant stabilizers, waxes, pigments, blowing agents, other flame suppressants and fillers such as carbon black, silica, barite, clays, wood flour, magnesium oxide , calcium carbonate, alumina trihydrate and the like. The preferred filler is calcium carbonate.

The known state of the art indicates that there is usually a direct * relationship between inhibition of smoke production and the amount of anti-smoke agent used, and that a greater amount of anti-smoke agent should result in a greater reduction in smoke formation, with all other factors remaining unchanged. In some cases, an applicable upper limit to the amount of anti-smoke agent is used. The upper limit is conditioned by additional factors such as cost, ease of mixing or interacting with. one other property of the mixture. In a particular case of the invention, it has surprisingly been found that there is no expected direct relationship between smoke production and the amount of anti-smoke agent.

In the case of zinc oxide plus a mixture of phthalate plasticizer and tri-melitane plasticizer, with a total plasticizer content of about 70 parts per 100 parts polyhalo vinyl vinyl resin, smoke production decreases rapidly when the amount of zinc oxide increases from 1 part to about 7 parts per 100 parts polyvinyl chloride, after which surprisingly smoke production increases when the amount of zinc oxide increases from about 10 parts to 30 parts per 100 parts polyvinyl chloride. For example, the preferred amount of zinc oxide is from about '2 to 30 parts per 100 parts polyvinyl halide, and the most preferred amount for minimal smoke formation is from 2 to 12 parts per 100 parts polyvinyl halide.

The compositions according to the invention can be used for all applications where polyvinylchloride plasticizers are used, including but not limited to coated fabrics, wire insulation and sheathing, wall coverings, etc. Examples of suitable fibrous backing materials are cotton fabrics, artificial fiber fabrics cellulose, felt, paper, polyester fabrics and mixed fibers mentioned. Fabrics can be coated by calendering, wrap, plastisol cover, on rollers, or by other methods known in the art.

In practice, zinc oxide as an anti-smoke agent, an antimony compound as a flame retardant and other components are combined with the resin in any manner by mixing.

In the following examples, all blends were prepared as follows, unless otherwise indicated:

The ingredients were mixed by hand, then for 10 minutes in a two-head differential crusher, with electric heating, maintaining a temperature of 150 ° G. The homogeneous mixture was formed under pressure at 160 ° C for 10 minutes, in a mold measuring 7.62 cm X 7.62 cm X 0.5 ohms, 3 X 6 X 0.020 *, under the total pressure of a hydraulic press with a pressure of 30 tons . To test for smoke production of various kits, the plates formed by compression molding from plasticized mixtures, as indicated above, were cut into samples measuring 7.62 cm X 7.62 cm and a thickness of about 0.55 cm. Each sample was placed in aluminum foil cut into dimensions allowing covering the front surface on all 4 sides.

The packaged sample was placed in a holder and burned in an Aminco NBS smoke chamber according to the instructions and in accordance with technical standard 708 NBS of December 1971. The amount of smoke was measured with a photomultiplier, calculating the correct optical density after correcting the soot remaining on the lens after the test. The measurement is made by determining the weakening of the light beam caused by smoke accumulated in a closed chamber during flame combustion. The results are expressed in terms of the specific optical density depending on the geometric factor of the incident light beam and the measured optical density (absorbance). This is the only measurement that characterizes the "smoke concentration" the most. The photometric scale used in this test method for measuring smoke is similar to the optical density scale for human vision.

The zinc oxide-free mixtures shown show maximum corrected specific optical densities of 400 or higher. By comparison, 10 parts of zinc oxide reduces this number to below 200. In the NBS study, a smaller number indicates less smoke. It should be emphasized that most of the values ​​for the maximum specific optical density of the sets are the average of 2 or more measurements of the tested samples of each set. Typically, two mixtures are considered to have different smoke production properties if the difference in maximum specific optical density is above 10.

103 567 ' .7

Further details regarding the reduction of smoke production are given in the following examples, where the composition of all mixtures is given in parts by weight per 100 parts of polyvinyl chloride resin, All mixtures contain 1.8 parts of barium-cadmium zinc stabilizer, 2.7 parts of epoxidized soybean oil and 0.2 parts of stearic acid, unless otherwise specified.

Example I. A blend containing 100 parts of polyvinyl chloride (Marvinol 22 from Uniroyal Inc.), 70 parts of dioctyl phthalate as plasticizer (DOP), 15 parts of calcium carbonate as a filler, 10 parts of antimony trioxide (Sb₂O3) and 10 parts of zinc oxide were mixed by hand, then kneaded in a two-round crusher for 10 minutes. The mix was pressurized into a 0.55 cm thick plate as described above. Two samples with an area of ​​3 inch were cut from the plate²) 7.62 cm X 7.62 cm and tested for smoke production in the Aminco NBS smoke chamber according to flame test.

' _t The above procedure was repeated except that zinc oxide was omitted.

_; The average maximum specific optical densities for these two mixtures were 176 with zinc oxide, 374 without zinc oxide.

Example II The procedure was analogous to that described in Example 1, using various plasticizers. The mixtures and smoke production results are presented in the following Table I. The plasticizers in the table are given according to their protective signs and are as follows:

Phthalate type:

Santicizer 711 - mixed alkyl phthalate with 7-11 carbon atoms.

ΡΧ-316 - mixed alkyl phthalate, higher percentage of linear alkyl radical than in Santicizer 711.

Phosphate type:

Santicizer 141 = 2-ethylhexyl diphenylphosphate.

Santicizer 148 = isodecyl diphenyl phosphate. Tri-titanium: Medium 70TM = · mixed alkyl trimelitate with 7-9 carbon atoms.

- The results in Table I clearly indicate that the introduction of 10 parts of zinc oxide extremely strongly reduces the amount of smoke produced by the mixture containing the flame retardant agent, antimony trioxide, regardless of the plasticizer.

Example III. The procedure was analogous to that described in Example 2, using different fillers to show that although there are differences in the total amount of smoke produced by a particular blend depending on the filler used and its amount, in each case zinc oxide acts as an anti-smoke agent. Maximum suppression of smoke was obtained when calcium carbonate was used as the filler. Mixtures and results are presented in Table II. 8

Table I

<td>Blend)</td><td>AND</td><td>B</td><td>C</td><td>D</td><td>E</td><td>F - \</td><td>G</td>

<td>polyvinylchloride vinyl</td><td> 100</td><td> 100</td><td> ) 100</td><td>and 100</td><td> 100</td><td> 100</td><td> 100</td>

<td>Zinc oxide</td><td> 0</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>Santicizer 711 ΡΧ-316 Śanticizer 141 Śanticizer 148 Śanticizer 79TM</td><td> 60</td><td> 70</td><td> 60</td><td> 60</td><td> 60</td><td> 60</td><td> 80</td>

<td>Calcium carbonate ,</td><td> 30</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td>

<td>trioxide antimony Maximal right</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>density optical</td><td> 378</td><td> 167</td><td> 160</td><td> 160</td><td> 162</td><td> 162</td><td> 195</td>

Table II

<td>Blend)</td><td>H</td><td>AND</td><td>J</td><td>K</td><td>L</td><td>M</td><td>N</td><td> 0</td><td>P</td>

<td>polyvinylchloride vinyl Oxide</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>

<td>zinc Oxide</td><td> 0</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>magnesium Carbonate calcium Tri-water oxide aluminum Santicizer</td><td> 30</td><td> 15</td><td> 15</td><td> 15</td><td> 20</td><td> 30</td><td> 15</td><td> 20</td><td> 30</td>

<td> 711</td><td> 60</td><td> 60</td><td> 60</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>DOP</td><td></td><td></td><td></td><td> 70</td><td> 70</td><td> 70</td><td> 70</td><td> 70</td><td> 70</td>

<td>trioxide</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>antimony Maximal</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td></td>

<td>right density optical</td><td> 378</td><td> 160</td><td> 163</td><td> 176'</td><td> 185</td><td> 172</td><td> 225</td><td> 204</td><td> 246</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td> ·</td><td></td><td></td><td></td>

Example IV The procedure is analogous to that described in Example 1 to determine the effect of the introduced anti trioxide⁵⁵ monu (Sat.₂ABOUT₃) for the production of dya by polyvinyl chloride mixtures. In combination with the plasticizer consisting of the mixed alkyl phthalate (ΡΧ-316) specified in Example 2 and the filler used in these mixtures,⁶⁰ nergism between zinc oxide and antimony trioxide regarding smoke suppression. Mixtures and results are presented in Table III. .

Example V. The procedure is analogous to that described in Example 1 in order to create a relationship between the content of zinc oxide 103 567

Table III

<td>Mixtures</td><td>Q *)</td><td>and ^R</td><td>S</td>

<td>polyvinylchloride vinyl</td><td> 100</td><td> 100</td><td> 400</td>

<td>Zinc oxide</td><td> 10</td><td> 10</td><td> 0</td>

<td>ΡΧ-316</td><td> 60</td><td> 60</td><td> 60</td>

<td>Calcium carbonate</td><td>¹⁵</td><td> 15</td><td> 15</td>

<td>trioxide antimony</td><td> 0</td><td> 10</td><td> 10'</td>

<td>Maximal right density optical</td><td> 225</td><td> 160</td><td> 349</td>

*) Instead of epoxidized soybean oil and Ba / Cd / Zn stabilizer, a tin stabilizer (Thermolite 31 - organocin mercaptycl) was used, in an amount of 2 parts per 100 parts polyvinyl chloride.

towards a smoke suppression. It should be emphasized that the effect of zinc on reducing smoke formation is complicated, because initially the reduction in smoke production progresses with an increase in the content of zinc oxide in the mixture, then quite surprisingly, above the optimal content of zinc oxide, i.e. from 5 to 12 parts by weight per 100 parts polyvinyl chloride, in a mixture containing about 70 parts of plasticizer per 100 parts of resin there is an increase in smoke formation.

Mixtures and results obtained are presented in Table IV.

to the one described in Example 1 from the following basic mixture:

<td>polyvinyl chloride</td><td> 100</td>

<td>Santicizer 711</td><td> 50</td>

<td>Santicizer 79TM</td><td> 20</td>

<td>calcium carbonate</td><td> 15</td>

<td>antimony trioxide</td><td> 10</td>

<td>zinc compound</td><td> 10</td>

The results obtained using various zinc compounds were as follows:

<td>compounds</td><td>Maximum specific optical density</td>

<td>AA zinc oxide</td><td> 137</td>

<td>AB zinc sulfate</td><td> 241</td>

<td>AC zinc sulfide</td><td> 318</td>

<td>AD zinc borate</td><td> 207</td>

<td>AE zinc nitrate</td><td> 208</td>

<td>AF not added</td><td> 333</td>

Example VII. The procedure was analogous to that described in Example 1 in order to demonstrate the effect of the mixture of a phthalate-type plasticizer and a triple-plasticizer on smoke production by a mixture containing the optimal amount of zinc oxide as a smoke suppressant and antimony trioxide as a flame suppressant. The observed synergism occurs at a weight ratio of phthalate plasticizer to trimelite plasticizer from about 6: 1 to about 1: 1.

Table IV

<td>Blend'</td><td>T</td><td>AT</td><td>V</td><td>IN</td><td>X</td><td>Y</td><td>FROM</td>

<td>polyvinylchloride vinyl</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>

<td>Oxide zinc</td><td> 0</td><td> 1</td><td> 3</td><td> 5</td><td> 10</td><td> 20</td><td> 30</td>

<td>Santicizer 711</td><td> 50</td><td> 50</td><td> 50</td><td> 50</td><td> 50</td><td> 50</td><td> 50</td>

<td>Santicizer 79TM</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td>

<td>Carbonate calcium</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td>

<td>Antimony</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>Maximum specific optical density -</td><td> 333</td><td> 241</td><td> 234</td><td> 142</td><td> 137</td><td> 176</td><td> 192</td>

Example VI. This example shows that many other zinc compounds either do not have the effect of inhibiting the production of smoke in mixtures with polyvinyl chloride, or much worse in comparison with zinc oxide.

Test plates were prepared using the analoTable V method

<td>Blend</td><td>AG</td><td>AH</td><td>AI_:</td><td>AJ</td><td>AK</td>

<td>polyvinylchloride vinyl</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>

<td>Zinc oxide</td><td> 10</td><td> 10 (</td><td> 10</td><td> 10</td><td> 10</td>

<td>Santicizer 711</td><td> 70,</td><td> 60</td><td> 50</td><td> 38</td><td> 0</td>

<td>Santicizer 79TM</td><td> 0</td><td> 10</td><td> 20</td><td> 38</td><td> 80</td>

<td>Carbonate calcium</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15^v</td>

<td>Oxide antimony</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>Maximum specific optical density</td><td> 176</td><td> 138</td><td> 137</td><td> 141</td><td> 190</td>

- Example VIII. Coated fabrics were made by mixing the coating compound in a two-circular crusher as in Example 1, after which a polyester / cotton knit fabric 85 g / m2 * was calendered with the coating compound in a known manner. The coating thickness was 0.3 mm (0.012 inch) at 150 ° C. The following mixtures were used to coat the polyester-cotton fabric:&gt; and.

1β £ Μ7

<td></td><td>LA</td><td>-AM *)</td>

<td>polyvinyl chloride</td><td> 100</td><td> 100</td>

<td>Santicizer 711 ⁷</td><td> 58</td><td> 50</td>

<td>Santicizer 79TM</td><td> 20</td><td> 20</td>

<td>calcium carbonate</td><td> 15</td><td> 15</td>

<td>afitimon oxide</td><td> 10</td><td> 10</td>

<td>zinc oxide</td><td> 0</td><td> 10</td>

<td>maximum specific</td><td></td><td></td>

<td>optical density</td><td> 165</td><td> 95</td>

*) Instead of Ba / Cd / Zn stabilizer, Thermolite 31 was used in an amount of 2 parts per 100 parts of resin.

. Example IX. By following the procedure described in Example 1, the following mixtures were mixed and tested in order to show that the synergism between zinc oxide and the tripellite plasticizer was kept within the concentration range of the plasticizer. Mixtures and results obtained are presented below in^f table VI. * &lt;

Table VI

<td>Blend</td><td>AN</td><td>AG</td>

<td>Polyvinyl chloride*)</td><td> 100</td><td> 100</td>

<td>Zinc oxide</td><td> 10</td><td> 10</td>

<td>Santicizer 711 '.</td><td> 40</td><td> 28</td>

<td>Santicizer 79TM</td><td> 0</td><td> 12</td>

<td>ChĆOj</td><td> 30</td><td> 30</td>

<td>SbtO,</td><td> 3</td><td> 3’</td>

<td>Maximum proper '</td><td></td><td></td>

<td>optical density '</td><td> 153</td><td> 116</td>

*) Polyvinyl chloride was stabilized with 5 parts per 100 parts resin with Tribase XL stabilizer (modified lead sulfate).

0.5 parts of Ross Waz 145 (paraffin) and 0.2 parts of Plastiflow POP (modified softened polyethylene) were used as a lubricant per 100 parts of resin.

Przykład.X. Operating in an analogous manner to that described in Example 1, the following mixtures were mixed and tested to demonstrate that the optimal zinc oxide content shown in Example V was reduced if the amount of plasticizer was reduced in the plasticized blend with polyvinyl chloride. Mixtures and obtained results are presented in the table VW._L

The results from Table VII indicate that:

SU With 20 parts of plasticizer per 100 parts of resin, the most preferred zinc oxide content is about 0.5-2 parts. ·. .

b. At 30 parts plasticizer per 100 parts resin, the most preferred zinc oxide content is about 2.0 parts.

. c. With 40 parts of plasticizer per 100 parts, the most preferred zinc oxide content is about 5.0 parts.

d. At 50 parts plasticizer per 100 parts resin, the most preferred zinc oxide content is about 10 parts.

• E. With 70 parts of plasticizer per 100 parts of Resin, the most preferred cynic oxide content is about 10 parts. Example XI. Proceeding in a manner analogous to that described in Example VIII coated fabrics: firstly manufactured by mixing the cover mixture on a two-core crusher as described in Example 1, then covering a knitted cotton fabric with a weight of about 136 g / m2² mix by calendering in a known manner. A coating thickness of 0.3 mm (0.012 inch) was adjusted at 150 ° C. The following mixtures were used and tested to cover cotton fabrics:

<td>Blend</td><td>BP</td><td>BQ</td>

<td>polyvinyl chloride</td><td> 100</td><td> 100</td>

<td>Santicizer 711</td><td> 60</td><td> 50</td>

<td>Santicizer 79TM</td><td> 0</td><td> 20</td>

<td>calcium carbonate</td><td> 15</td><td> 15</td>

<td>antimony trioxide</td><td> 10</td><td> 10</td>

<td>zinc oxide</td><td>and</td><td> 10)</td>

<td>maximum specific optical density</td><td> 122</td><td> 89</td>

The above example demonstrates the synergistic mixture of a phthalate-type plasticizer and a triple-plasticizer during smoke production by a mixture containing an optimal amount of zinc oxide as a smoke suppressant, calcium carbonate as a filler and antimony trioxide as a flame suppressant.