DE2743624C2 - Flame-retardant and smoke-resistant, halogen-containing plastic compound and process for its production - Google Patents

Description

Plastic materials, including plastic sheet, synthetic fibers or the like, are used in the General Regarded as hazardous materials in terms of their flammability. It is common practice to add various flame retardants to the plastic materials. Lately one looks at But the tendency of plastics to develop a lot of smoke when burned is at least as dangerous or even more dangerous than your flammable wedge. The serious consequences of numerous fires are on the due to strong smoke formation, which prevents timely leaving of the building concerned due to severe visual obstruction.

Thorough investigations were carried out with regard to additives which delay flame formation and the spread of flames in the case of halogen-containing plastic compounds. Examples of such additives are Antimony trioxide, antimony oxide, anilmonoxide / silicate oxide, and other organic and inorganic antimony compounds. Zlnkboral has also been used as such a substance, but generally does not serve as a • »o a means of suppressing smoke; besides, it was always in a relatively large amount of z. B. 3 to 8 parts per 100 parts of plastic are used, since smaller amounts do not cause flame retardancy.

US Pat. No. 3,723,139 describes the addition of anllmonoxide in combination with sodium antimonate to polyvinyl chloride in order to keep its flammability and smoke formation to a minimum.

From US-PS 39 45 974 a halogen-containing plastic compound is known which contains zinc salts in an amount of 0.2 to 1 part, calculated as zinc oxide, per 100 parts of polymer for smoke suppression.

If such zinc compounds are used in a concentration in excess of the aforementioned values for flame and smoke retardancy and were originally produced by conventional high-temperature processes, they tend to degrade the plastic compound in which they are incorporated. Such a connection with which the breakdown takes place quickly. Is zinc oxide.

si) DE-OS 21 33 061 reports on additives for synthetic resins, in particular for polyvinyl chloride. The additives consist of an active and an inert part. The active part can, for example, be formed from an oxide, several oxides, a basic compound of zinc, calcium or magnesium or a mixture of such substances as basic compounds of calcium-zinc . The inert part of the additives is a synthetic resin. z. B. polyvinyl chloride. According to the specified mixing ratios, the proportion of the powdery active component is at least 16.6% by weight. With these additives, the problem of providing a lubricious and non-dusting stabilizer for synthetic resins should be solved. In this context, there is no question of a flame retardance or similar properties.

The invention is based on the object of specifying flame-retardant and smoke-resistant ι · »halogen-containing plastic compounds, the thermal stability of the plastic compound should not be impaired

This Aulgabe crflndungsgcmäß is achieved by a plastic mass, from 0.25 to 10 wt ^ ^1. a solid solution containing zinc oxide and magnesium oxide and / or calcium oxide, 0.1 to! O parts by weight of magnesium oxide and / or calcium oxide, based on 1 percent by weight of zinc oxide, being present. (^ Preferable catfish contains 0.5 to 10% by weight of the solid solution.

In addition, it has proven to be particularly advantageous if the plastic compound additionally contains 0.1 to 10 Parts by weight of Antlmonirioxld, based on 1 Gcwichistcil of the solid solution contains.

The plastic compositions identified in claims 2 to 7 are particularly preferred.

In addition to zinc oxide, the plastic compositions according to the invention also contain magnesium oxide in the solid solution and / or calcium oxide in order to give the zinc oxide sufficient heat stability. It means that the polymer in the plastic compound does not discolour at temperatures of up to around 200 or 210 ° C. This makes this possible the processing of plastics, the polyvinyl chloride and other halogen-containing polymer systems include, e.g. B. the production of films and other objects as well as rolling and extruding.

Very different plastics can be used as the basic component of the plastic compositions according to the invention Question. Mostly it is hard and soft polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, Polystyrene, polyester and Acrylnllril-butadlene-styrene copolymers, each containing a halogen. The expression "halogen-containing plastic compound" means both those compounds that are used a halogen-containing polymer, such as polyvinyl chloride, were obtained, as well as those compositions which, although iu using a halogen-free polymer such as a polyester prepared, but then with a halogen-containing compound have been added. Corresponding halogen-containing compounds are Decabromdlphenyloxld and perchlorpentacyclodecane, as well as a chlorinated polyethylene with a chlorine content of about 65%, a melting point of over 350 "C and a particle size of 5 to 15 μm. Such compounds are generally in an amount of about 10 to 35 wt. V, preferably about 12 to 25 % By weight, based on the polymer, added.

A real solution is a homogeneous mixture of two or more substances, which shows several characteristic properties, such as the dissolution down to the molecules as well as the absence of sedimentation phenomena and fixed proportions of the components. The best known examples of solutions are solids dissolved in liquids. But there are also solutions of liquids in liquids and of solids in solids. For example, an empirical phase diagram of a ZnO / MgO system was published, which shows that there are two solid boundary phases, the pearl class solution, based on a MgO smoothing surface (cubic NaCl smoothing device), and the zinc oil solution, based on the hexagonal ZnO -Wurtzit-Gltter (EM Levon et al, "Phase Diagram for Ceramists, 1969, Supplement", corresponding to the NBS. 1969. Published by the American Chemical Society, p. 87, Flg. 2312, System MgO-ZnO, and JDH Dunay ^ and HM Ondlsh, "Crystal Data", 3rd ed., Vol. 2, Inorganic Compounds, published by JCPOS, ZnO, H-1.5965, data of a solid solution of MgO-ZnO).

According to the invention it has been found that ZnO / CaO and ZnO / CaO / MgO systems are also solid solutions can form. Solid solutions such as ZnO / MgO / solutions have also been found to be effective agents for flame and smoke retardancy. . ">

The solid solutions of zinc oxide and magnesium oxide and / or calcium oxide according to the invention are prepared by thoroughly mixing of ground zinc oxide with ground magnesium oxide and / or calcium oxide, in the desired proportions and calcining the mixture at a temperature of about 500 ^C C up to about 1500 ° C. preferably at 800'C to 1000 ° C. The magnesium oxide and / or calcium oxide and the zinc oxide can in the dry state or in the form of a wet, pasty mass with each other. be mixed. Technical grade reagents can be used as purity is not critical. Magnesium oxide, calcium oxide and zinc oxide can be added in the form of their carbonates, hydroxides or other compounds which disintegrate in oxide compounds during calcination. So z. B. Limestone or slaked lime can be used as a Calclumoxldqucllc.

Exact measurements of the lattice parameters were made on plastic compounds according to the invention by X-ray measurements. performed to demonstrate the presence of solid solutions in these masses. A standard diffraction meter was used to obtain the 2-thcta spectrum from X-ray diffraction. The measurement conditions were as follows:

1) 2-theta spectral range: 6 ° to 145 "

2) KV / Ma: 45/35

3) gap: Γ

4) Paper feed 75.90 cm / h

5) Goniometer speed: 1 / 4'7Mlnutc

6) Estimated accuracy of line measurements: ± 0.005 "5n

7) Inner standard for correcting the 2-theta peak position: KCI powder crystals

The information in the following table I represent the gliterparanieier (a ", c") for five mixtures Contained 60 wt .-%, magnesium oxide and 40 wt .-% zinc oxide and calcined under various conditions became. The lattice parameters clearly show the formation of a solid solution in all five samples. The lattice extent of both magnesium oxide and zinc oxide are in accordance with the published Declarations:

The shift in the smoothing parameters (a, "c") for both the CaO / ZnO and ZnO / MgO / CaO systems (see Table II) shows that the solid solution is formed during the calcination of these systems. The CaO / ZnO system contained 60% by weight of CaO and 40% by weight of ZnO and was calcined for 2.5 hours at 950 ^; C **. The ZnO / MgO / CaO system contained 18% by weight. ",, ZnO, 41 parts by weight" ,. MgO and 41 wt% of CaO and ■ was. culclnlert for four hours at 900 "C.

An increase in the calcination temperature of the oxide mixture, which leads to the formation of the solid solution according to Invention was used, e.g. B. from 500 to 1000 ° C, led to a significant decrease in the specific Surface of the solid solution. This is well known. However, it had not yet been found that the capacity- <5 of a substance that suppresses the formation of flames and smoke !, with the specific surface area sees. Oxygen index measurements on a semi-solid polyvinyl chloride show e.g. B. a corresponding decrease with reduced specific surface. To a lesser extent, the power of the solid solution was also increased

weakened to reduce smoke formation. Thus, the effectiveness of the flame retardancy and the Smoke suppression of the solid solution according to the invention both with the formation of the solid solution as together with the specific surface area of the particles. The following table HI shows information about a system which contains 40% by weight of zinc oxide and 60% by weight of magnesium oxide, with at different temperatures was calculated.

Table 1

Sample (% by weight> Calcination MgO ZnO

Temperature time grid parameters *) grid parameters

( ⁰ C) (h) a "(A) a" (A) c "(A)

40 ZnO / 60 MgO 900 4.5 4.22791 not calculated 40 ZnO / 60 MgO 950 0.50 4.21854 not calculated 40 ZnO / 60 MgO 1000 0.25 4.22048 not calculated 40 ZnO / 60 MgO 950 0.50 4.21703 3.25102 5.20902 40 ZnO / 60 MgO 900 8th 4.21228 not calculated pure MgO - - 4.213 - - pure ZnO _ _ 3.249 5.205

*) based on the sharpness of 2-Theia angles. where the equivalent sharpness a "± 0.00006 Ä isl

Table U

Sample (weight%) CaO MgO ZnO

Lattice Pdranielcr *) Gillerpuranicter *) Lattice Parameler *) a "(A) a" (A) a "(A) c" (A)

60CaO / 40ZnO 4.80894 - 3.25113 5.20674

18ZnOMlMgOMlCaO 4.80901 4.22157 not calculated

pure CaO 4.8105 - -

pure MgO - 4,213 - -

pure ZnO - - 3.249 5.205

*) based on the sharpness of 2-thcta-angles. where the iiquivalcmc sharpness is a "+ 0.00006 A.

It is generally desirable to calcine the mixture at a temperature and for a period sufficient to form a solid solution with a specific surface area of over 10 mVg, preferably of over 16 m ^; /G. Especially from over 30 m ^! / g, is sufficient. Cooling times of several hours, e.g. B. from about 15 minutes to about 10 hours are preferred; they depend on the temperature.

The smoke measurements were made in the smoke density chamber in accordance with the National Bureau of Standards. Plates from a rolled stock material with an area of 19.35 cm 'and a thickness of 0.102 cm were used as test specimens. The tent In required to achieve a 90% maximum density (T90) Minutes and the corrected maximum amount of smoke for deposition on the chamber walls (Dme) measured to calculate percent smoke reduction. Oxygen index values were determined according to the Method according to ASTM-D2863 determined, where Piobekodies 150 χ 6.5 χ 3 mm 'were used. the Heat stability In PVC bet 190 "C was made by rolling the samples with the plastic or other plastic additives obtain. The test pieces were cut out from the rolled plate and a certain Tent heated to 190.5 ° C. They were removed from the heating device after certain time intervals taken out, and the color of the plastic compound was compared with that of the specimen, none Contained additives. Brown discoloration was considered a defect. The tent in minutes, after which if the deficiency set in, it was recorded and compared with the tent of a standard sample that did not contain any additives and showed the deficiency after 45 minutes.

Further solid solutions according to the invention of ZnO / MgO, ZnO / CaO and ZnO / MgO / CaO were effective in inhibiting the formation of flames and smoke. Optimal properties were obtained with the ZnO / MgO system when the solution was about 30% by weight of ZnO and 70% by weight. MgO contains up to about 50 wt.% ZnO and 50 wt.% MgO. The ZnO / CaO system is obtained with optimal properties when the solid solution contains about 50% by weight of ZnO and 50% by weight of CaO to about 85% by weight of ZnO and 15% by weight of CaO Optimal properties in a ZnO / MgO / T'aO system are obtained when the solid solution contains about 10% by weight to f'Ua 60% by weight, ZnO. 10 to 60% by weight of ¹ V MgO and 5 to 50% by weight of CaO.

The examples illustrate the invention.

Example !

40 g of zinc oxide and 60 g of magnesium oxide were carefully mixed in a mixer. The zinc oxide as well the magnesium oxide was added as a powdery material.

The mixture was transferred to a ceramic tube and during the entire calcination step a> subject to slow tumbling motion. The mixture was heated to 950 "C and at that temperature calclnlert for four and a half hours. After the calcination was completed, the mixture was cooled and passed with a hammer mill through a 0.5 mni grinder to break up the agglomerates that were formed during the formation of the solid solution of the mixed oxides.

The obtained solid solution of zinc oxide and magnesium oxide was made into a conventional one PVC sheet containing 1.5% antimony oxide given. The amount of the solid solution added was 2% (corresponding to 0.7% zinc oxide). Various tests have been carried out using this product to show its advantages. The percentages relate to weight.

The oxygen index was 37.7, the smoke reduction had a value of 36'Ί> and the heat stability was 5 minutes lower than that of the control sample without additive (Table! V). ι?

About the effect of different calcination temperatures and thus also that of the specific surface To determine the solid solution, various mixtures were calibrated at different temperatures. Table III gives the oxygen index and smoke reduction achieved using this Systems have been achieved again.

In these tests, the plasticized PVC sheet was prepared using the following approach: o manufactured.

Table III

sample Calcining
tcmperature ( ⁰ C) Calcination
/ cil (St. Oil percentage
Smoke min
change specific
surface
m - '/ g 40 ZnO / 60 MgO 500 8th 39.8 40 50.3002 40 ZnO / 60 MgO 750 8th 38.1 41 30.7351 40 ZnO / 60 MgO 900 8th 36.2 33 16.1514 40 ZnO / 60 MgO 1000 8th 34.4 34 3.6814 Components Parts

PVC, inherent viscosity 1.13 100 (ASTM D1755, classification GP-6-15443), mean molecular weight / weight average = 150,000

DOP (di- [2-iilhylhxyl] -phlha! Al 23.5

Epoxidized soybean oil 1.5

Ba-Cd stabilizer 2.0

Stearic acid 0.5

Antimony trioxide 1.5

ZnO-MgO and / or CaO as indicated

40

50

Example 2

For this example, 989 grams of magnesium oxide and 598 grams of zinc oxide were added to 6 liters of deionized water. The slurry was 21% solids.

After stirring at room temperature for half an hour, the solids became under vacuum filtered off. The filter cake was dried in an oven at 120 ° C. for 18 hours. The dried one Filter cake was broken up and calcined in a ceramic rotary tube. After reaching a temperature from 900 ° C the batch was calcined at that temperature for four and a half hours. After cooling down the solid solution was passed through a 0.5 mm grid using a hammer mill to remove agglomerates break up. The data are presented in Table IV.

Controls A through C

To the superiority of a solid solution of magnesium oxide and zinc oxide compared to a not To show calcined mixture of magnesium oxide and zinc oxide became a control experiment (Control A) carried out in which a non-calcined mixture of these two oxides in the same weight ratio as in

60

65

Example 1 was used. If in this particular experiment the mixture to the ordinary PVC was given, the heat stability was very poor; H. 20 minutes less than the standard PVC product, that did not contain any additives. This poor heat stability was equal to that obtained when zinc oxide alone (Control B) was used as an additive (without magnesium oxide).

Another control experiment (Control C) was performed on the magnesium oxide and zinc oxide separately (i.e. 8 hours at 900 "C) calclnleri and the two calcined oxides then mixed. If This mixture was used in a plastic plate, the etch stability was good, but the percentage was Smoke reduction very bad. The data are also presented in Table IV along with the in values obtained for controls A and B are shown.

lu

Examples 3 to 7

The solid solution according to the invention to inhibit the formation of flames and smoke was also used compared to a magnesium zinc sulfate complex salt. It was found that, despite the fact that the ii The heat siabiiiiäi, the oxygen index and the smoke reduction were satisfactory, the complex salt, when it has been incorporated into the plastic. Gas and bubbles formed, which is undesirable. According to the invention However, the solid solution used did not give rise to gas or bubbles when in a plastic material came into use.

In these experiments, various solid solutions of zinc oxide and magnesium oxide and / or Calcium oxide prepared by dry mixing the specified approaches and during the tent and at the temperature given in Table IV and then used in conventional PVC.

Example% MgO% CaO

3 83.8

4 73.5

5 4.8

6 - 60

7 35 35

3> The results are given in Table IV. The test results were satisfactory in all examples with the exception of the smoke reduction according to Example 5 (low MgO content).

Examples 8-11

Various zinc and magnesium compounds were used as starting materials in these experiments used.

In Examples 8 to 10, the zinc and magnesium compounds were selected in the form of their hydroxides aqueous solutions precipitated by adding sodium hydroxide. These hydroxides were then in turn calcined to form solid solutions of magnesium oxide and zinc oxide. In Example 8, salts were in the form of chlorides used as starting materials, while nitrates in Example 9 and zinc and magnesium sulfate In the example IO were used.

In Example 11, an intermetallic alloy of zinc and magnesium (Mg ₂ Zn) was used as the starting material. A solid solution of zinc oxide and magnesium oxide was formed during calcining. In all of these experiments, satisfactory results were obtained, as can be seen from Table IV.

Although the resistance of a plastic compound to flame and smoke is improved when particles a solid solution of zinc oxide as well as magnesium oxide and / or calcium oxide was present in the mass found that further improvements can be achieved if Aniimonoxld is also in the plastic compound is present.

Therefore, the solid solution was made from zinc, magnesium and / or calcium oxide and antimony oxide. The amount of antimony oxide added to the zinc, magnesium and / or calcium oxide was Im generally between about 0.05 to 15 parts, preferably about 0.1 to 10 parts. Antimony oxide per part the solid solution (all parts are by weight).

Table IV Example no.

% ZnO ¹ M ₁ MgO XC-M Culcination

Zeil temples) nilur (° C)

Heat oxygen percentage

Stability index. Smoking

(niin little reduction

ger than
Default)

1 ZnO / MgO (dry mix) 40 60 4 V: 950 5 37.7 36 2 ZnO / MgO (wet mix) 37.7 62.3 - 4 '/ 2 900 10 38.3 36 control A ZnO / MgO not calcined 40 60 - 0 0 20th 38.9 44 B ZnO alone 100 - - 0 0 20th 35.5 42 Calcine C ZnO MgO separately 40 60 - 8th ΙΛί \ Γϊ
7 \ Y \ J 10 34.6 19th Example no. 3 ZnO / MgO 16.2 83.8 - 8th 900 10 35.0 28 4 ZnO / MgO 26.5 73.5 - 8th 900 5 34.8 30th 5 ZnO / MgO 95.2 4.8 - 8th 900 10 34.4 10 6 ZnO / CaO 40 - 60 2 ¹ A 950 10 37.0 37 7 ZnO / MgO / CaO 30th 35 35 4th 900 10 36.3 34 8 ZnCl ₂ / MgCl ₂ hydrolyzed 40 60 - V / i 950 5 37.9 31 9 ZnNO ₃ / MgNOj hydrolyzed 40 60 - V / 2 950 .S 38.0 40 IO ZnSOa / MgSO ^ hydrolyzed 40 60 - V / 2 950 5 38.3 29 ! 1 Zn / Mg (intermetallic 45.8 54.2 - V / 2 950 5 38.3 29 Alloy)

The additives were added to the plastic in amounts equivalent to 0.7% zinc oxide and 1.5% linear oxide

It has also been found that the resistance to flame and / or smoke in some Cases can be increased slightly if different amounts of other agents are also added to the zinc oxide and magnesium oxide and / or calcium oxide are added to the solid solutions. These funds are including zinc borate, aluminum aluminum hydride, molybdenum oxide and other common additives for inhibition the formation of flames and smoke.

From the above description and the present examples it is clear that a halogen-containing w Plastic compound that has a low percentage of solid solution of zinc oxide and magnesium oxide and / or contains calcium oxide, has a particular resistance to flames and smoke. Under Use of the solid solutions according to the present invention to reduce the flame and Smoke formation gives very good results compared to agents that contain only zinc oxide. Contains mixtures of zinc oxide and magnesium oxide and complex compounds of MgO and zinc salts.

Example 12

A solid 40/60 ZnO / MgO solution, which was produced in accordance with the method described in Example 1 steiii was incorporated into an approach for a pipe from Hartpoiyvip.ylchlorld. The determined the following results:

The approach continued in parts by weight as follows together:

(A) (B) (C) PVC, inherent viscosity 0.92 100.0 100.0 100.0 (ASTM D-1755 classification 6P-4-16 043) average Molecular weight / Weight average = 91,000 stabilizer 0.5 0.5 0.5 Paraffin wax (73.9 ° C) 1.0 1.0 1.0 Calcium stcanite 0.7 0.7 0.7

(Λ) (B) (C) flexible, stiff lubricant,
modified polyethylene wax,
specific temperature (at 25 ° C)
(),%, Melting point 116 ° C 0.15 0.15 0.15 Caleiumearbonal 2.5 2.5 2.5 TiO; 1.0 1.0 1.0 Sb ₃ O. 0 0 2.0 / nO / MgO 0 0 2.0 SauerslolTindex,
ASTM D-2863A 48.7 58.4 66.9

NBS smoke density, 0.09 cm material, Low flame conditions

- "Dm (per g, corrected) 50.0 38.6 32.7

Percentage reduction 0 23 35%

Example 13

The solid solution is very effective when used in conjunction with phosphate plasticizers. When a 40/60 ZnO / MgO solid solution was prepared according to the method described in Example 1 and incorporated into PVC for thread and cable using a phosphate welder, the following results were obtained:
", Approach (Gcwichlslcilc):

(A) 5 L. - (B) (C) (D) (U) (H) PVC, intrinsic viscosity 100 - - same same sity 1.02 (ASTM 24.9 D-1755. Classifi 15th cation GP-5-15443), 15th Average mole 0.2 gross weight / 52 Weight average = 100,000 - Lead silicate sulfate, - same same - - 64.0% PbO, specif cal weight 3.9 electrical quality - same same - - Calcium carbonal - same same - - POP - same same - - mixed dialkyl 52 26 26th 26th 26th phihalat Tricresyl phosphate - 26th 26th - - Alkyldiarylphosphai - - - 26th 26th Sb ₂ O ₃ 5 - - - Zno / MgO 4th 4th - 4th Oxygen index, 30.6 28.3 28.5 27 ,! 1 27, ASTM D-2863A

NBS smoke density.
0.09 cm material,
Flame conditions

_fi5 Dm (per g, 50.1 35.9 66.1 39.6 54.6 32.4

corrected)

percentage 0 28 0 40 0 41

reduction

Example 14

Very small amounts of the solid solution are effective in controlling the smoke in the case of a high impact polystyrene suppress. If a fcsic 40/60 ZnO / Mp () solution according to the procedure described in Example 1 and was incorporated into the polystyrene, the following results were obtained:

Approach (weight):

(A) (B) (C) high impact polystyrene 85 same Decabromodiphenyl oxide, 10 same POP 0.5 same Sb ₂ O ₃ 5 4.75 4.75 ZnO / MgO 0 0.25 0.75 NBS-Rauchdichie, 0.06 cm material, Lambing conditions Dm (per g, corrected) 118 108 95 Percentage decrease 0 9 20 UL 94, vertical burn test V-O V-O V-O

Example 15

Small amounts of the solid solution are effective in suppressing smoke from polypropylene. When a Solid 40/60 ZnO / MgO solution prepared according to the method in Example I and incorporated into the polypropylene the following results were obtained:

Approach (Gcwichlteilc):

(Λ) (B) (C) Polypropylene, nominal 60 60 60 Melt Flow I ₂ (at 23O ⁰ C) 6.5 chlorinated polyethylene, 65% Cl 27 27 27 Particle size 5-15 µ. Melting point> 350 ° C Sb ₂ O, 13th 12th 10 ZnO / MgO 0 I. 3 NBS smoke density, 0.06 cm material, Flammability conditions Dm (per g, corrected) 43.7 37.7 34.9 Percentage decrease 0 14th 20th

Example 16

The solid solution is very effective in Acrylonitrll-Butadlcn-Slyrol-Copolymerlsatcn (ABS). When a solid 40/60 ZnO / MgO solution was prepared according to the method in Example 1 and incorporated into ABS, the following results were obtained:

27 43 Sb ₃ O ₃ 624 (B) (C) (D) ZnO / MgO (Λ) 12.3 4th 4th SECTION 12.3 3 0 3 Lead chlorosilica complex, 0 61.3 82 82 64% PbO 61.3 2 2 2 chlorinated polyethylene 2 tricyclic bromine complex, 24.4 0 0 29% Br and 40% Cl 24.4 0 12th 12th Oxygen index. 0 ASTM D-2863 A 29.6 25.0 24.2 NBS smoke density, 26.0 0.04 cm material, Flammability Conditions Dm (per g, corrected) Percentage decrease 78.8 117 91.8 84.8 7th 0 22nd 0

Example 17

Μ \ The solid solution lsi very effective when used in conjunction with or Antimontrloxld Alumlnlumoxldirihydrat (ATH) used in a semi-solid polyvinyl chloride (PVC). If a solid 40/60 ZnO / MgO solution was prepared according to the method described in Example 1 and PVC was incorporated together with SbjOi or ATH, the following results were obtained:

Sowing? (Parts by weight):

(Λ) (H) (C) (D) (E) (F)

PVC gcmälJ example 1 K) O Dcundccyl phthalate 30th dibasic blister stabilizer, 7th PbO 79.8%, specific Weight 4.5 fatty diamide, 0.3 synthetic wax two basic blcist carat. 0.3 55.3% PbO Sb.iO, - ZnO / MgO - ATH - Oxygen! ndex. 27Λ ASTM D-2863 Λ NBS smoke seal c. 0.09 cm material. Fm flame conditions Dm (corrected per μ.) 73 Pm / enual reduction 0

32.1 28.1

same same - same same - same same - same same - same same - 2 _ _ 2 - 2 - 20th 18th 34.1 30.1 30.8

75.7 39.3 4 (1.1 53.6 39.9

(+ 3) 46 45 27 46

Example 18

Small amounts of solid IAs are used to suppress smoke in halogenated polyesters (HPE) effective. When a 40/60 ZnO / MgO solid solution was prepared using the procedure described in Example 1 and was incorporated into HPE, the following results were obtained:

Approach (Gewiclusicile):

(Λ) (B), "

HPE, halogenated polyester, own 100 100

shafts at 25 ° C: acid number 18, color (Gardner) maximum 5, Brookfield

Viscosity 400 (50 rpm, spindle no. ^2)?

1100 (5 lipm. Spindle no. 2) methyl ethyl kelon peroxide Sb ₃ O.,

ZnO / MgO "' ^: "

Oxygen Index, ASTM D-2863A

NBS smoke density, 0.165 cm material, flammable conditions Dm (per g, corrected) Percentage reduction

Example 19

The solid solution works synergistically with Anllmontrloxld. If a 40/60 ZnO / MgO solid solution prepared by the method described in Example 1. When used in conjunction with Sb ₂ Oi in a semi-rigid polyvinyl chloride (PVC), the flame retardancy measured by the oxygen index test was greater than would have been expected by adding the effects of Sb ₂ O. and ZnO / MgO, as the following information demonstrate.

The batch from Example 1 was used, the data denoting the weighting point.

I. 1 5 5 0 I. 43.3 43.4 57.6 44.5 0 23

ticwichtslcile PVC 100 DOP 23.5 Epoxidized soybean oil 1.5 Ba-Cd stabilizer 2 Stearic acid 0.5 Sb ₂ O, (χ), ZnO / MgO (y) χ + y = 2

Addition to χ and y (weight level)

Sb ₂ O ₃ 40/60 Ol Dm *) (per g, percentage

ZnO / MgO corrected) Min

change

2 5 O 32.9 39.0 0 i. 0.5 34.6 - - 1 I. 34.5 21, X 44 O N US Rauc 2 33.7 19.0 51 • ι llnmmcns hiluhlc. 11/11 '> cm Miitci Ul. Kalintuii igen ties

From the foregoing description and examples, it is clearly shown that a halogen-containing Plastic compound that has a low percentage of a solid solution of zinc oxide as well as magnesium oxide and / or contains calcium oxide, a great resistance to the action of flames and smoke and their formation inhibits bz *. suppressed. Using the solid solution will produce results scores that iUid better than those made with zinc oxide alone. Mixtures of zinc oxide and magnesium oxide and complex compositions of magnesium oxide and zinc salts can be obtained.

Claims (8)

Patent claims: 1. Flame-retardant and smoke-resistant, halogen-containing plastic compound, characterized in that they contain 0.25 to 10% by weight of a solid solution of zinc oxide and of Magnesium oxide and / or calcium oxide, with 0.1 to 10 weight points magnesium oxide and / or Calcium oxide, based on 1 part by weight of zinc oxide, are present. 2. Plastic compound according to claim 1, characterized in that it also contains 0.1 to 10 parts by weight Contains antimony trioxide, based on 1 part by weight of the solid solution. ^{3. Plastic compound according to spoke 1} , characterized in that the solid solution is about 50 to 35 to wt .-% zinc oxide and about 15 to 50 wt .- 1 *. Contains calcium oxide. 4. Plastic compound according to claim 1, characterized in that the solid solution is about 30 to 50 Contains weight percent zinc oxide and about 50 to 70 weight percent magnesium oxide. 5. Plastic compound according to claim 1, characterized in that the solid solution is about 10 to 60 Contains weight percent zinc oxide and 5 to 50 weight percent calcium oxide. 6. Plastic compound according to claim 1, characterized in that the solid solution has a specific surface area of about 10 m ² / g. 7. Plastic compound according to claim 1, characterized in that the solid solution has a specific surface area of more than 16 m ^J / g. 8. A method for producing a plastic composition according to claim 1, characterized in that one W a mixture of zinc oxide and magnesium oxide and / or calcium oxide at a temperature of over 500 "C to a solid solution and this solid solution is worked into a halogen-containing plastic after a grinding process, the final plastic mass 0.25 to 10 wt .-% of the solid solution and about 0.1 to 10 parts by weight of magnesium oxide and / or calcium oxide, based on 1 part by weight of zinc oxide, are used.