Polyvinylhalogenide mixture with reduced formation of smoke at burning

Plasticized polyvinyl halide polymer blends with reduced smoke formation on combustion are known which contain 2 to 30 parts of zinc oxide.

Zinc oxide has previously been commonly used in polyvinyl halide resins as a stabilizer (U.S. Patent No. 3,446,765), as a pigment (U.S. Patent No. 2,682,484), and as a stabilizer for non-co-promoters (U.S. Patent No. 3,041,193).

Specific materials exposed to forced combustion release smoke and toxic gases that are dangerous to fire because they exacerbate the possibility of leakage, cause injury, reduce survival and prevent fire. The latest statistics show that around half of fatal accidents in incidental fires are caused by smoke, and not by heat or burning. There is a need to develop synthetic organic materials with as little properties as possible! releasing smoke. These materials are particularly needed for the cladding of airplanes, ships, motor vehicles and home interiors, as well as in the manufacture of furniture and the like.

It is known that large amounts of black smoke are released when the polyvinyl halide ear is burned. Soil fillers, such as dloethyl phthalate, emit more smoke than ophthalmic analogs. From the viewpoint of burning prevention, there are worthless substances for polyvinyl halides, such as tin, lead, magnesium, manganese, tellurium, titanium, copper, greyhound, aluminum, vanadium and tungsten, because they can smoke. It has been found that antimeoint oxide, which is commonly experienced as a flame retardant of polyvinyl halide compounds, can often cause an increase in smoke generation. during forced combustion.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyvinyllialogenide mixture with. reduced smoke generation when burned.

This goal is achieved with polyvinyl halide benders - pelyvinyl halide stabilizer and plaetifier in the range of 60 to - 80 haotnoetal - parts per 100 parts by weight of poly (vinyl halide)₉ which is characterized in that it contains 1 to 30 parts of zinc oxide together with 10 parts by weight of antimony trioxide and 15 to 30 parts of ultrium (calcium or 15 parts of magnesium oxide) to 100 parts h ^ c ^ oi ^ (^ E ^ tt ^: eheh - parts of p ^ J ^ jy ^ jLn ^ JLel ^ lor ^ du · x)

The present invention is capable of obtaining - substantially β-suppressed - - fume formation upon combustion - with properties highly desirable for safety. According to the present invention, there is an improvement in the safety of the memorials that are used for constructions.

Hereinafter, the present invention is described in more detail. The concepts of smoke generation during combustion and the release of smoke during forced combustion are identical.

The compositions according to the invention expediently provide zinc oxide in a quantity of 2 to 10 parts by weight or 5 to 12 parts by weight per 100 parts by weight of polyvinyl chloride parts.

Polyvinylhrlcgejidtvé srnOsi ^ β ^^ ίο! antimony compounds and antimony compounds as flame retardant, 1 to 30 parts by weight of zinc oxide. Preferably, it is a mixture of tlcelllellitate and antimony trioxide as the preferred antimony compound.

Suitably, the polyvinyl halide blends comprise calcium carbonate or magnesium oxide, which acts as a synergistic filler.

PolyvinylHalogenide resins used after polymers, copolymers and copolymers of polymers. Examples - easy to use. polyvinylheltggenidcwýeh - pryeksriřLc are:

1. Halo-polymers such as potyrilium chloride, polyvinyl bromide, potyrilide, potyrilide chloride, polydichlorostyrene and the like;

2. Copolymers such as vinyl acetate, vinyl chloride, vinyl chloride, vinylidene, vinyl starch, vinyl chloride diethyl oleate copolymer and vinyl chloride-ester copolymer, wherein the ester is formed from - unsaturated alcohols and unsaturated alcohols and;

3. They are composed of poly (III) chloride and poly (III) stearate, sweat (III) chloride and vinyl acetate / vinyl chloride copolymer and polylyl chloride, poly (III) chloride and poly (III) diethyl maleate copolymer and the like.

The resins may be treated with china as a smoking-retardant by any conventional means. In some instances, anti-sweating can be easily achieved by treating one or more surfaces of a plastic wax with an additive resin additive, such as when a surface is treated by coating, i.e., by coating or impregnating with an additive. In a similar way, - textile products of all types and - constructions - can be coated with a layer or - with a thin film - of the additive compound.

Suitable filters for the above-mentioned types of resin, in particular for the above-mentioned particles, are generally in the range of from 30 to 100 parts by weight per 100 parts by weight of polyvinyl chloride. high boiling esters such as (2-ethyllexyl) piperazine, Ms (2-ethylhexyl), diethylene glycol diethers, dippypylene glycol, ethyl acetate, acetic acid - n-iitylcitlate, - epoxy soybean oil, -2-ethylbutylglutol acetate, diethylene glycol diphenyl acetate, oeetllftallletlylglliolate, 1- (2-ethylhexylphosphate), tris (2-ethylhexylphosphate), trituttxyethyl (11-phthalic acid), tert-phenyldiophenyl (2-ethylphthyl) phthalic acid (2-ethylphenyl) phthalic acid, 2-ethylphenylphosphate, 2-ethylphenylphosphate, 2-ethylphenylphosphate, 2-ethylphthalate, 2-ethylphthalate, 2-ethylphthalate; α-β-thiophthalate, dimethylsulphide 203150 phthalate, B 1 (2-ethylhexyl) ft.^andsubstances, n-octyl-n-dimethyl phthalate, isooctyl aleyeyl phthilate, dlisedesilicate, ditridecyl trilate, biphenyl calf, iedesyl lbenyl phthalate, polyesters · idipic acid (mol. wt. 2200), polyesters · iseliinic acid (mol. wt. 1500); (mol. hi. 800), methylricinoleate n-butylacetylricinoleate, bls (2-ethylhexyl) sebacate, tatylicetoxystearate, phenylsulfonate alkyl sulfonates and tri (2-1 / 11,11) (1) triaellitate.

Other suitable zinc-zinc-containing plistifiers include (54% chlorine) biphenyl, hydrogenated fluids, polyalkylene naphthenes, chlorine (24% to 70% chlorine) ··lecrine, · N-cyclopentyl-p-toluenesullonamide polymers · clay conjugates. % of which is less than 7 ethers of carbon, such as butadiene, with a polymerizable monomer, such as acrylonitrile or neboidе Уρρρρρρρρ. .

It has been found that a particularly effective plistifier for the release of smoke is a blend of a plist-ificatoxil of the phthalate type and a tristelite plistifier. A mixture of these two plistiffs in weight. % to about 6: 1 to about 1: 1 produces a synergistic side effect when combined with zinc oxide, both smoking and intense, as well as burning.

In general, an improvement in the flame resistance of the composition of the invention can be achieved by introducing into it a metal compound wherein the metal is an intem, irsenic or absorbent in the pickling from 1 to 30%. of this polymer blend. The invention is preferably used in a mixture of inttaonium oxide. However, many other compounds of intimacy are also suitable.

Suitable compounds of the internal include, but are not limited to, intemmonium sulfides, Group I salts of the Periodic Table, intimonium salts of organic acids as well as pentavalent derivatives thereof and intimonium acid esters and derivatives thereof. It is customary for the compositions according to the invention to use sodium intimonitin or potassium nitrite if it is desired to ingest the ilkilic antimony salts. U.S. Patent 2,996,528 discloses suitable intimate organic acid salts 8 and pentavalent derivatives thereof.

Compounds of this class include bityl, rolled, ciproate, heppylate, ciprylate, phirgonate, capiret, ηϊοοϋ »», intiMun enisate and their dihilogen derivatives. Similarly, the mono-ester esters and their penetrant derivatives are disclosed in U.S. Pat. No. 2,993,924 and are, for example, tri (n-ethyl) intl, tri (2-ethylhexyl) -malt, α, α, α, α, α, α, α, α, The tris (beta-chloroethyl) trans-tri- (beta-chloropyridine) intimoontone, their pentavalent di-derivative derivatives.

Still other suitable orginic compounds with vinegar are cyclic derivatives of lithium lithium, such as trimethylolproplontiminol, tannone and glycine tinnitine. Also, the opioid compounds of both irsen and vimut, especially oxides of these metals, may be used.

The other ingredients which may be seen in the polyvinyl halide sauces of the present invention include light and heat, waxes, pigments, additives, flame retardants, flame retardants, such as size, silica, talc, wood, wood, wood, wood. flour, burning oxide, calcium carbonate and the like. When the filler is provided with magnesium oxide or calcium carbonate, there is a synergistic reduction in smoke release.

Previous physics indicate that there is usually a direct relationship _? among scho] plia zibxrtait smoking and masculine used smoke-burning ingredients, usually with more smoking-enhancing ingredients, a greater metal-епП is achieved if the other factors remain the same. In some cases, the upper whitefly of the smoking agent is particularly used. This upper spike is the basis for eclectic fictors, such as ceoi, ease of mixing or interference with some other plaque. subasrate.

Particularly in the case of the present invention, it has been unexpectedly discovered that only a direct dependence between smoking prevention prevails in the amount of smoking prevention additive. In the case of zinc oxide and a mixture of phthalate plasticizer and trimellittt plasmicizer, the total plasticizer content of about 70 parts per 100 parts of smoke release decreases rapidly as the zinc oxide rises to about 7 parts per 100 parts of polystyrene chloride and then unexpectedly increases in release. % of zinc oxide from about 10 parts to 30 parts, based on 100 parts of polyvinyl chloride.

As the content of the plaque increases, the optimum concentration of zinc oxide also increases. The preferred zinc oxide is from 3 to 30 parts, based on 100 parts of poly-4-vinyl halide, and particularly preferred grit for minimal smoke release is 2 to 10 parts, based on 100 parts of polyoloyl halide, when the plasticizer content is 30 to 50 parts, and is 5 to 12 parts when the plasticizer content is 50 to 100 parts.

The formulations of the present invention can be used in applications where polystyrene halides are suitable but are not comminuted, such as coated fabrics, wire and cable insulation, and sheathing, wallpaper, and the like. Examples of suitable fibrous backing materials for fabric coating are cotton and viscose fabrics, felt, paper, polyester fabrics and blends of previous materials. Teetles can be coated by cladding, cast coating, rolling, or any other method well known to those skilled in the art.

In practicing the present invention, zinc oxide, such as a smoking additive, an antimony compound, a flame retardant, fillers, and other components of the mixture may be mixed into the mixture by any suitable mixing technique conventional in the art.

In the examples below, all mixtures are made, unless otherwise stated, as follows:

The ingredients are first mixed by hand and then for 10 minutes on a two-roll electrically heated differential mill maintained at 150 ° C. HomogeeH! the mixture is then melted in a hydrotreated use at 30 tons for 10 minutes at 160 ° C under full pressure. Forms 7.62 x 15.24 x 0.06 cm are used. In the smoke discharge test of the various compositions, the test specimens of 7.62 x 7.62 x about 0.06 cm were cut from the molten mix plates as above. Each sample is spilled onto an aluminum foil, cut to size, which allows the sample areas to be redrawn from all four sides. The wrapped sample is placed in the holder and panned in the Amine smoke chamber of the NBS · - according to supplementary instructions and according to NBS Technical Report 708 of December 1971.

The amount of smoke is helping! fžtžoátžbičr. The optical density is wasted and then correlated on the carbon black of the armor on the lens at the end of the test. Measurements are made by attenuating the beam of light absorbed by the smoke in a closed chamber used for flame combustion. The results are expressed with respect to the specific optical density, which is derived from the generic factor and the measured optical density (adsorbe). This is a simple measurement of oejchatrtkeriiSicic smoke concentration. (Fc) Trimeric scale - used to measure smoking in this test method is similar to the optical density scale for human observations.

The network without addition of zinc oxide provides a corrected maximum optical density - in the range of 400 - or more. To compare 10 parts of the oxide, it shrinks - this number to less than about 200. In the NBS test, the smaller the number, tm shows less smoke. It should be noted that most of the specific smmsi density values ​​are averages from measurements taken on two or more test samples at each site. Generally, two networks are used as if they had different atmospheres of smoke if the difference in the math-specific optical density is greater than 10.

Further details on reducing smoke evolution are given in the following examples, wherein all components are given in parts by weight per 100 parts of polyvinyl chloride resin. All blends contain 1.8 parts barium, cadmium and zinc stabilizers,

2.7 parts epoxidized soybean oil and 0.2 parts stearic acid unless otherwise stated.

Example 1 p

Mixture containing 100 parts by weight of polyvinyl chloride (Marvinol 22 from Uniroyal, Inc.), 70 parts by weight of dioctyl phthalate plasticizer (DOP), 15 parts by weight of calcium carbonate as a filler, 10 parts by weight of antimony trioxide (Sb2O4) and 10 parts by weight of zinc oxide. mix manually and then grind on a two-roll mill for 10 minutes. The mixture is poured under pressure into plates with a thickness of about 0.06 cm as previously described. Two 7.62 cm square square samples are then cut from the plates and the smoke evolution in the Amineo NBS smoke chamber is tested using a combustion test.

The above procedure is then repeated, omitting zinc oxide.

The average maximum specific optical density for both mixtures is as follows:

with zinc oxide 176 without zinc oxide 374

Example 2

The procedure of Example 1 was repeated using different plasticizers. The mixtures and smoke release results are shown in Table 1 below.

The plasticizers listed in Table 1 are designated by protected names as follows:

Phthalate type

Santicizer 711 = mixture of (C 1 -C 4) alkyl phthalates

PX-316 = a mixture of alkyl phthalates, higher percentage of linear chains than Santicizer 711

Phosphate type

Santicizer 141 = 2-ethylhexyldiphenylphosphate

Santicizer 148 = isodecyl diphenyl phosphate

Trimellitate type

Santicizer 79 ™ = mixture of (Cy-Cg) alkyl trimellitates

The results in Table 1 clearly show that the introduction of 10 parts by weight of zinc oxide remarkably reduces the amount of smoke released from the antimony trioxide composition as a flame retardant regardless of the plasticizer.

Table 1

<td>Mixture</td><td>AND</td><td>В</td><td>C</td><td>D</td><td>E</td><td>F</td><td>G</td>

<td>polyvinyl chloride</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>Santicizer 711</td><td> 60</td><td> 70</td><td></td><td> 60</td><td></td><td></td><td></td>

<td>PX-316</td><td></td><td></td><td> 60</td><td></td><td></td><td></td><td></td>

<td>Santicizer 141</td><td></td><td></td><td></td><td></td><td></td><td> 60</td><td></td>

<td>Santicizer 148</td><td></td><td></td><td></td><td></td><td> 60</td><td></td><td></td>

<td>Santicizer 79TM</td><td></td><td></td><td></td><td></td><td></td><td></td><td> 60</td>

<td>calcium carbonate</td><td> 30</td><td> 15</td><td> 15</td><td>¹⁵4</td><td> 15</td><td> 15</td><td> 15</td>

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

<td>optical density</td><td> 378</td><td> 161</td><td> 160</td><td> 160</td><td> 162</td><td> 162</td><td> 157</td>

Example 3

The procedure of Example 2 was repeated using different fillers. It turns out that although the differences in the absolute amount of smoke released in the individual compositions depending on the filler and its amount, zinc oxide acts as an anti-smoking additive in all cases. Maximum smoke suppression is achieved when calcium carbonate is used as a filler.

Mixtures and results are shown in Table 2.

Table 2

<td>Mixture</td><td>H</td><td>AND</td><td>J</td><td>К</td><td>L</td><td>M</td>

<td>polyvinyl chloride</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>magnesium oxide</td><td></td><td></td><td> 15</td><td></td><td></td><td></td>

<td>calcium carbonate</td><td> 30</td><td> 15</td><td></td><td> 15</td><td> 20</td><td> 30</td>

<td>Santicizer 711</td><td> 60</td><td> 60</td><td> 60</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>antimony trioxide</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

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

<td>optical density</td><td> 378</td><td> 160</td><td> 163</td><td> 176</td><td> 185</td><td> 172</td>

Example 4

The procedure of Example 1 is repeated to determine the effect, including antimony trioxide (Sb 2 O 4) on the release of smoke from the polyvinyl chloride mixtures. With the mixed alkyl phthalate plasticizer (PX-316) described in Example 2 and the filler combination used in these mixtures, it achieves a synergistic effect between zinc oxide and antimony oxide with respect to smoke reduction.

Mixtures and results are shown in Table 3.

Table 3

<td>Mixture</td><td>N +</td><td> 0</td><td>P</td>

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

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

<td>PX-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>antimony trioxide</td><td> 0</td><td> 10</td><td> 10</td>

<td>Maximum specific optical density</td><td> 223</td><td> 160</td><td> 349</td>

+ A tin stabilizer (Thermolite 31 - organotin mercaptide from MAT Chemical Corp.) was used, 2 parts per 100 parts, instead of epoxidized soybean oil and a Ba (Cd) Zn stabilizer.

Example 5

The procedure of Example 1 was repeated to demonstrate the relationship between the zinc oxide concentration and smoking suppression. It should be noted that the effect of zinc oxide to reduce smoke release forms a complex showing an initial decrease in smoke release with an increase in the amount of zinc oxide and then unexpectedly shows an increase in smoke release above the optimum amount of about 5-12 parts per 100 parts of polyvinyl chloride a mixture containing 70 parts per 100 parts plasticizer.

Mixtures and results are shown in Table 4

<td>Mixture</td><td>Q</td><td>R</td><td>WITH</td><td>T</td><td>no</td><td>IN</td><td>w</td>

<td>polyvinyl chloride</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> 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>calcium carbonate</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td>

<td>antimony trioxide</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> 321</td><td> 226</td><td> 251</td><td> 163</td><td> 156</td><td> 170</td><td> . 192</td>

Example 6

This example shows that many other zinc compounds are either ineffective as a smoke suppressant for polyvinyl chloride mixtures, or definitely worse than zinc oxide.

Test plates are prepared according to the procedure described in Example 1 from the following basic components:

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

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

<td>Santicizer 79RM</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 for the various zinc compounds tested are:

Compound

Maximum specific optical density

<td>X</td><td>zinc oxide</td><td> 156</td>

<td>Y</td><td>Zinc sulphate</td><td> 241</td>

<td>of</td><td>zinc zinc</td><td> 318</td>

<td>AA</td><td>zinc borate</td><td> 207</td>

<td>AB</td><td>nitrate. zinc</td><td> 208</td>

<td>AC</td><td>none</td><td> 321</td>

Example 7

The process of Example 1 is intended to provide some of the synergistic effect of phthalate-type plasticizer and trimellulose plasticizer on releasing smoke from mixtures seeking optimum amounts of zinc oxide, as a smoking additive and antimony trioxide additive. The observed synergistic effect is demonstrated at a weight ratio of phthalio plasticizer to iricyllate plasticizer of about 6: 1 to about 1: 1.

Table 5

<td>Mixture</td><td>AD</td><td>AE</td><td>AF</td><td>AG</td><td>AH</td>

<td>polyriin chloride</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>Ssarticizer 711</td><td> 70</td><td> 60</td><td> 50</td><td> 38</td><td> 0</td>

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

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

<td>antioxidant oxide</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>specific optical density</td><td> 161</td><td> 153</td><td> 156</td><td> 145</td><td> 137</td>

Example 8

The coated fabrics were prepared by blending the coating on a two-roll mill as in Example 1, and then the mixture was calendered to a 33.9 g / m 2 knit of polyester and cotton using a stantartite. A coating of 0.03 cm thickness at room temperature is used^plot^E 15⁰ Deň: 32 ° C.

To coat the knitted fabric of polyester and cotton, the successor sss is used. Until these values ​​happen. smoking:

<td></td><td>AI</td><td>AJ +</td><td>AK</td>

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

<td>Searticizer 711</td><td> 50</td><td> 50</td><td> 60</td>

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

<td>calcium keyite</td><td> 15</td><td> 15</td><td> 15</td>

<td>antioxidant oxide</td><td> 10</td><td> 10</td><td> 10</td>

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

<td>Maalmmetric specific optical density</td><td> 165</td><td> 89</td><td> 122</td>

Pebernmlit 31 (2 parts per 100 parts) is used in place of Ba (Cd) Zn of the tablet.

Example 9

This example shows that the optimal amount of zinc oxide, as shown in Example 5, will increase when the amount of plasticizer in the plasticized polyvinyl chloride mixture increases.

The results are shown in Table 6 below.

Table 6

Total plastic content - Optimum concentration of zirconium (parts per 100 parts) zinc oxide (parts per 100 parts)