DE1694414A1 - Fire-resistant polyolefin - Google Patents

Description

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PATENT Attorney DIPL.-ING. RICHARD MÜLLER-BÖRNER PATENTANWALT DIPL.-ING. HANS-HEINRICH WEV BERLIN-DAHLEM ■ PODBIELSKIALLEE 68 MUNICH 22 ■ WIDENMAVERSTRASSE TELEPHONE: 76 29 07 - TELEGRAMS: PROPINDUS TELEPHONE: 22 SS 88 · TELEGRAMS! PROPINDUS

19 072

Johnson & Johnson
501 George Street

New Brunswick, Uew Jersey (V, St. AO

Fire-resistant polyolefin.

The invention relates to a polyolefin which is particularly resistant to open flames.

A lot of plastic objects like those in electronics and used in electrical applications in industry, commercial engineering and households it is important that the to their manufacture materials used have flame resistance. Above all, the polyolefins are of interest in this regard, especially in the case of textiles, since the Filaments made from such polymers because of their many desirable chemical and physical properties extensive possibilities for the production of the most diverse Open finished item. However, it is so far

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TELEPHONE) 0184087

169441 *

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failed to develop additives for polyolefins, by which guarantees a satisfactory fire resistance of the polyolefins »

When selecting such an additive, especially those for further processing and use of the important properties of polyolefinic synthetic resin, such as its color, flexibility, tensile strength, electrical properties, Softening point etc. not or only to an insignificant extent Dimensions can be reduced or abolished »So far, however, it has not been possible to find a usable fire-resistant To develop polyolefin without at the same time the desired original properties of the polyolefinic resin were adversely affected. Although it is for example known that many halogens and / or phosphorus-containing compounds cause certain flammable substances Give fire resistance. However, with many substances, especially with polyolefins, it has not been possible to achieve one Finding a way to incorporate such additives into the polymers in such amounts that the required fire resistance is achieved without the additionally desired original properties of the plastic be affected.

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The object of the invention is to solve the aforementioned difficulties to overcome and create a fire-resistant polyolefin made from a polyolefin compound consists, to which an organic bromine compound is admixed. This is done according to the invention by means of a dispersing agent for the organic bromine compound admixed with the polyolefin compound to its essentially uniform Dispersion achieved within the polyolefin, the polyolefin compound generally being a polyolefinic material, such as any polyolefin or the like. can be.

Here is under the designation "dispersing agent" for the purposes of the invention to understand a dispersing agent that the formation and stabilization of the dispersion of a predetermined substance in another.

In the case of the polyolefin according to the invention, it is for the dispersing Means particularly important that it is very well tolerated with the organic bromine compound used in each case is, in particular to a sufficient extent at the temperatures required for forming the polyolefin, e.g. the injection temperature, so that the additives contained in the polyolefin are avoided, also the dispersing agent must be at the use temperature of the threads made from the polyolefin

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or other items. ·. sufficiently compatible with the be organic bromine compound so. Excretions or Migration of the substances contained in the polymer plastic can be avoided.

The dispersing agent is used in the inventive Polyolefin, the active additive, ie. the organic Bromine compound increases rapidly and effectively substantially uniformly within the amorphous portion of the polymer distribute without its crystalline part being dissolved or in any way preventing appreciable crystallization of the polymer. The dispersing agent used according to the invention must have these merits and must also allow the organic Bromine compound from the amorphous part of the polyolefin compound is absorbed because these two compounds are not compatible with one another or dispersible in the other. Therefore, the dispersing agent must work with both, viz

the polyolefin compound and the organic bromine used be and the organic bromine compound

connection / easy to disperse within the polyolefin compound « It also has to be resistant, which means in particular that it has a low vapor pressure and a low vapor pressure Have diffusion rate within the polyolefin got to. '. . "■ - '" · -

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Examples of dispersing agents which satisfactorily meet the aforementioned conditions are chlorinated polyphenyl compounds consisting of diphenyl or eriphenyl compounds containing from about 20 to about 70% by weight of chlorine or mixtures of chlorinated biphenyls or triphenylene, which contain about 20 to about 70 % chlorine. Particularly suitable chlorinated polyphenyl compounds are chlorinated biphenyl with 60 wt .-% chlorine, chlorinated triphenyl with 60 wt -.% Chlorine content and a mixture of chlorinated biphenyl and chlorinated Iriphenyl with 65 wt .-% chlorine content or the like. Further examples of useful dispersing agents which satisfactorily meet the aforementioned conditions are chlorinated caphthalene, stearic acid, and paraffins and the like.

The dispersing agent should be contained in the composition of matter in amounts of approx. 0.05 to approx. 20% by weight based on the total weight of the resulting polyolefin, preferably between 5 and 10%. The exact range of proportions depends on the particular dispersing agent used. For example, chlorinated biphenyl in amounts up to 20 wt -.% Are used, occur without the exudates, whereas when using it

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of stearic acid "already" at concentrations of about 1% leads to excretions which "become so significant at concentrations of more than 4% that the use of stearic acid in such concentrations is prohibited. According to the invention, more than just a single dispersant can be used Agents are used, but the total amount of dispersing agent must be kept within the limits given above At concentrations below about 0.05%, there is insufficient dispersing agent in the polyolefin to perform the required functions described above. then there is also the aging of the resin to discharges of organic bromine compound contained therein, and when spraying the crowd unpredictable problems may occur. for economic reasons, it does not make sense to use the dispersing agent in additions of more than about 20%, because the degree of leuer resulting from such additional amounts resilience is more than enough. In addition, a larger proportion of dispersing agent in the polymeric mixture causes a deterioration in the other favorable properties of the polyolefin.

With regard to the special requirements for the active fire-resistant additive, i.e. the organic bromine

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Connection, was "in the work that led to the invention have found that the fire-resistant additive a) resistant to water and "weathering must be, b) must not contain water and must have a sufficiently low vapor pressure so that the plastic is injected can be without gassing, c) a good thermal stability in the case of the injection of the polyolefin must have the fuel temperature to be used, d) with the polyolefin compound can be made compatible at the injection temperature and at the use temperatures must, so that it does not separate or precipitate from the polymeric substance, e) contain a high content of bromine should, so that a small amount of the fire-resistant additive is already effective because of the addition a significant amount of additive is undoubtedly the desired one Would destroy or impair properties of the polymer, and f) non-reactive with the starting polyolefin the injection temperature and also not substantially reactive or unstable at ignition temperatures, so that the flame is extinguished or a fire is made more difficult, " and therefore essential features of the invention are ,, .Typical Examples of such compounds are organic bromophosphate and tris-2,3-dibromopropyphosphate of the formula

BrOH ₂ OHBrOH ₂ O \
.BrOH ₂ OHBrGH ₂ O -P = O
'BrCH ₂ OHBrOH ₂ O /

These conditions are created by the organic bureau connections fulfilled, which are used according to the invention as active additives

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The organic bromophosphates are the "preferred active" ones fire-resistant additives according to the present invention.

It is important that the organic bromine compound, on the one hand, creates a fire resistance and, on the other hand, also has sufficient thermal stability and, at around 200 ⁰ G, a sufficiently low vapor pressure so that it does not gas or react with the starting polyol in the spreading device, total £> can be scratched. It appears that when the bromine of the organic bromine compound reacts with the polyolefin resin, many desirable properties of the polyolefin are lost. ".

As the well-known organic bromine compounds that increase the fire resistance effect of the polyolefin according to the invention, are not compatible with the starting polyolefins, is the addition of a specific dispersing agent as defined above within the The above-described additional quantity ranges are extremely important. Lie without the use of this dispersing agent namely the achievable concentrations of fire-resistant organic bromine compounds in the polyolefin

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below what is required to achieve the required fire resistance of the synthetic resin necessary concentrations, and also the required uniform distribution of the organic bromine compound in the polyolefin is not guaranteed.

If the polymeric substance mixture according to the invention is to be used in thread form in the end product, then "the fire-resistant bromine compound must be present in amounts of approx. 3 to approx. 12% by weight, based on the total weight of the polyolefin according to the invention, preferably approx - 'up to 8% at a concentration of about 5 to 6% elemental bromine. With these amounts of additives, a 0.3 mm thick stretched monofilament thread extinguishes in less than one second after an ignition period of three seconds. Below a proportion of 3 % is not enough fire-resistant additive present in order for the required fire resistance is achieved. Above about 12% experiencing technical difficulties affecting the degree of chemical compatibility, and it is clear unwanted polymerization. If flammable dyes are present, must The lower limit can be raised; in this case a minimum addition of about 35 ° / ° Q-Is has proven sufficient en.

When specifying the percentage range from 3.0 to 12%, this is more necessary organic bromine compound is assumed to be

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the organic bromine compound contains at least more than 2 % to about 8% elemental bromine. At a content of less than 2% is not enough elemental bromine is present to impart van the polyolefin resin, the desired fire resistance, and more than approximately 8 ^c / o the resulting resin generally is no longer meltable. The aforementioned concentration limits apply to the fact that threads produced from the synthetic resin are to be processed into fabrics in which both the warp and the weft threads consist of a polyolefin according to the invention. However, in the case in which only the warps or only the weft threads consist of a material which contains the fire-resistant additive or if less than practically all threads of the fabric made from the polyolefin contain the fire-resistant additive, the lower required limit for the content must be of elemental bromine can be increased to 5%.

If, on the other hand, the polyolefin is to be brought into a form other than thread form, i.e. if less surface area per unit mass is exposed to the oxygen in the air and thus it becomes difficult in the one formed from the artificial hara Object to reach a high mass temperature, the mass fraction of organic bromine used

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binding, but this connection still has to be be present in sufficient quantities to meet all requirements, which are described in the introductory part. The occurrence of a loss of specific surface area in relation to the The shape of the thread is easy to see in the case of a film or a cast object, for example, which has less surface area per unit of mass comes into contact with the air and thus with the oxygen than with a thread. This fact promotes the fire retardant Effect because less oxygen is available to cause the entire object to catch fire. Still owns such a shaped object has a larger cross-section than normally a thin thread, and thus it becomes, there little-surface is exposed to heat, difficult ,, a To achieve such a high mass temperature, i.e. such a high temperature in the polymeric plastic exposed to heat, as it is normally necessary to kindle a band. Therefore, in such cases, the advantages of the

only

lying invention already achieved when / approx. 1 % .an organic bromine compound is contained in films from 0.13 to 0.18 mm thick and in cast or otherwise shaped objects of at least the same thickness.

In any case, if necessary, and you can within the concentration ranges mentioned above in relation to threads and shaped objects,

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also more than just a single organic bromine compound than May be used, but the total amount " -an organic bromine compounds that form the polymeric substance are added, in accordance with the limits "as they are for the use of only one organic bromine compound were specified.

If the threads to be produced from the polyolefin according to the invention are to be dyed, then about 0.1 % to about 3 % of inorganic dye or carbon black, based on the total weight of the disfiguring material, can be added to the system of substances Premix or can be added to the injection molding compound. Although, in general, all types of carbon black can be used in the polyolefin according to the invention without impairing the fire resistance produced or other desired properties of the polyolefin synthetic resin, it must be ensured that the carbon black used is compatible with the overall system and that it does not react with other components of the system or with any additives contained therein. For best results, a carbon black concentrate premix is preferably prepared, ie a premix containing carbon black, a small amount of the synthetic resin. which it is to be mixed, dispersants for the soot in the mixture and a small amount of other

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certain neutral substances that are used to achieve good results used contains. The latter substances must and may be compatible with the overall substance system do not react with the other additives.

The stability of the mixture for the spraying operation can be improved by adding as little as 0.05% of stearic acid based on the total weight of the mixture. Here it is essential that no more than 4 % is added, because this addition acts in the sense of increasing the flammability of the product at higher concentrations. Preferably about 0.5% to about 1 % are added; However, since the stearic acid also acts as a dispersing agent, the requirements with regard to the amounts by weight to be added are to be kept in accordance with those which have been described above with regard to the dispersing agent be included in the mixture, either together with other dispersing agents or alone.

The presence of stearic acid is therefore essential for the injection process Well worth it because the stearic acid makes it obvious the spindle of the injection molding tool is kept clean and .Reactions in the injection molding device that occur as a result of contact sub-

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punching could be prevented.

Although a mixture of the components mentioned here, ie the organic bromine compound and the specific dispersing agent (with or without stearic acid) can be injected, it is not sufficiently compatible with the polyolefin to allow it to be absorbed in the grains of the synthetic resin by means of a heat curing technique in an oven to be surface-absorbed at 150 ⁰ G for JO minutes to several hours. It is therefore expedient to use the starting pole volefin synthetic resin in flake or powder form and to premix it according to a method consisting of the following steps: a) Mixing a mixture consisting of a predetermined polyolefin synthetic resin, a dispersing agent and an organic bromine compound in a suitable mixer, e.g. a vibration mixer, so that a free-flowing mixture is created which can be fed in through the filler neck of the spray device and continues to run through the spray device without interruption. It is appropriate that the mixing is carried out at "room temperature, ie at 27 ° C or below, and that both the synthetic resin and the additives are at a temperature of 27 ° G or less before mixing, so that a complete wetting of the individual particles is prevented, which would otherwise lead to a loss of the good flow properties of the mixture.

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The mixing time should only be on for the same reason limited to a few minutes. The premix can be made into pieces if desired.

The mixture of the organic bromine compound and the dispersant Means is used together with the polyolefin particles or flakes and possibly other additives for the injection molding process, the * layer casting, the casting sen, etc. to a temperature within heated in the range from approx. 175 C to approx. 245 ° C, because at this temperature the mixture is easily absorbed into the polymeric synthetic resin. Below 175 ° G is the Recording speed very slow, and the results are generally not worthwhile because of the penetration, or the Almost complete absorption of liquid into the polymeric substance due to its amorphous regions, but the polyolefins are highly crystalline at room temperature. Heating the polymeric substance reduces its crystalline properties Structure and creates the desired amorphous areas. The heat to be applied to the polyolefins should be in Such amounts are added that one is sufficiently below the melting point of the particular polymer used The substance remains so that you can be sure that the special condition of the synthetic resin is retained and thus the free-flowing properties this intermediate mixture ensured

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are, whereby the handling of the "mixture" in the up to Finished product is facilitated following process steps,

The addition of dispersing agents does one rapid and complete diffusion of the particles of the active fire-resistant organic bromine compound and leads for its faster, even dispersion in the entire mass of the polymeric substance, so that a uniform Finished product is achieved.

When adding the dispersing agent to the organic Bromine compound, these two parts are mixed so well that a practically homogeneous mixture is created.

The mixture is then made with the special starting polyolefin brought together, and the mongrel proportions are again thoroughly mixed, so that a practically even distribution the proportions within the resulting mixture of substances is ensured. In this latter mixing process it is it is particularly important to disperse the constituents in such a way that this creates a synthetic resin mixture that certainly enables a uniform polymer material to be sprayed, so that the fabric areas are within the polymeric fabric not in their chemical or physical properties "

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differentiate it from other neighboring or more distant areas of material. In the same way it is important to be excessive Mixing should be avoided, because this removes the individual particles of the polypropylene are wetted and in this way the good pleating properties of the synthetic resin mixture are reduced. This is because a good, free-flowing charge is desirable for the spray device, so that spraying is uniform is achieved without interrupting the load by bridging in the filling opening of the spray device.

The spraying is carried out at about 205 ° C, but the useful temperature range for this is between about 190 0 and about 245 ° C. A splash substantially below 190 ⁰ G leads to melt fracture in the polymeric material, and syringes substantially above 24-5 0 causes an undesired and destructive reaction between the polymeric material and the other constituents.

The polymer material emerging from the spray device is cooled and then heated to about 150 0 to align by stretching to become. In this way there is an improved tensile strength of the polymeric substance. Ideally, the stretching is done in a ratio of 6: 1, however a range of about 4: 1 to about 8: 1 has proven to be

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proved satisfactory. It's easy to see that a Variation of the stretching ratio a corresponding variation the tensile strength achieved "

The spraying of the mixture should be at a temperature that is not more than about 24-5 G, must be completed, because above this temperature an undesirable reaction between the organic bromine compound and the polyolefin can occur which together with a total or partial loss of strength of the polymeric substance can lead to an impairment or a reduction in other desirable properties.

It is possible that the temperature of 245 C after or is exceeded during the spraying process, but in this case the dispersing agent or must have the dispersing Agents within the dex polymer system. Kind of preventing the organic bromine compound from to collect and in the polymeric substance larger mass concentrations to form so that this is not present in a number of "places in such a concentration that is sufficient, to initiate a reaction between the bromine of the fire-resistant additive and the polymeric polyolefin. In in this case the selected dispersing agent may be one as defined above, as well however, one can be used that

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the tendency of the bromine from the fire-resistant Additive to 'calm down, with that which forms the basic substance polymeric starting polyolefin to react.

As already stated above, it is advisable to that the starting polyolefin is in partial form, i. e. in powder or flake form, because in this form the additives can be easily distributed in the polyolefin. Of the Polyolefins are preferably the poly-oC-olefins used, i.e., those polyolefins whose all saturations are in the state of a monomer. Such polymers are characterized in that they have a configuration in which either all of the substituting groups, apart from Hydrogen, above or below the main chain line of the polymer. Examples of such polyolefins are polyethylene, polypropylene, poly-1-butene and copolymers of these connections. Especially for the application in the frame preferred polyolefin of the present invention Polypropylene because of its very desirable chemical and physical properties.

Namely, because of this, it is desirable that the polyolefin resin in particle form, i.e. in flakes or in granular form exists because in this physical state there is a, -.

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has the largest possible surface. This promotes and supports the good mixing of the dispersing agent and the fire resistant organic bromine compound in the Polyolefin synthetic resin. Since the organic bromine compound and the Polyolefin resin usually incompatible with each other the resulting difficulty can be circumvented, for example, by making sure that that at least the minimum amount of fire-resistant additive is dispersed within the polyolefin resin is.

As an alternative solution, however, a surface coating can also be used provided on a molded article made of polyolefin; In any case, a dispersing agent or the Combination of dispersing agents can be selected so that the incorporation of at least the minimal amount of fire-resistant additives in the polymer or at least in the immediate surface layer of the polymer will. This difficulty is circumvented when the fire-resistant additive hits the surface of the Object is simply painted on and he is here in this penetrates in sufficient quantity and from the polyolefin object is added, so that "in this way a relatively permanent protective coating is created.

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It can, aticli, give a poryolefin composition, which has a very much improved resistance against decomposition due to exposure of the polyolefin to sunlight and weather conditions. For this purpose a system of predetermined selected stabilizers in amounts between about 0.1 and about 9% by weight, based on the weight of the entire polymer composition. A corresponding proportion of such stabilizers can also be added to the polyolefin according to the invention are attached to this one essential increased resistance to weather conditions and decomposition by ultraviolet light to lend. The stabilizers of this type are ultraviolet light absorbers, antioxidants and heat absorbers <>

Upon closer inspection of the eligible. Ultraviolet light absorbers the part of the sunlight spectrum is of particular interest, i.e. that part of the ultraviolet range, which is sufficiently energetic to break chemical bonds, i.e. to photochemical decomposition of the; Polyolefin articles to effect. In the present invention, the ultraviolet light absorbers must be limited to such that are compatible with the special polyolefins used here. These are for example p-octyl-phenyl-salicylate, 2-hydroxy-4-n-octoxybenzophenol, and substituted acrylics; one under the

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Han.deΊs name AM-101 well-known organic nickel complex and tert-butyl salicylate. The ultraviolet light absorber can be used in amounts of from 0 to about 5 GeW ₀ - exist% in the final product. If the effect caused by the ultraviolet light absorber is particularly desired, the useful concentration limits are between approx. 0.25 and approx. 5% by weight.

The anti oxidizing agents included in the present Invention come into consideration must also be at the injection temperature and use temperature with the polyolefin compounds be compatible, i.e. they must not be eliminated and they must also have a sufficient level Heat resistance at the injection temperature in question have so that the polyolefin according to the invention can be injected. You must also have a ' Have color stability, i.e. little or no color changes during or after spraying or during the life of the polymer to be considered cause. Furthermore, they must have a very good resistance own against the action of water, so they cannot be leached out of the end product by moisture, because otherwise the desired tensile strength and oxidation resistance would be nullified. Examples of anti-oxidants that

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meet these conditions are 2,6-di-tertiarybutyl-pcresol; ÄÖ.-1095, "Irganox 565 ', 858, 10? 6 and 1093, which are commercially available under this name;" Santanox ", a dialkyl oxenol sulfide known under this trade name, a -j : 1 condensate of a J-methyl-e -tertiary-butylphenol with Grotonaldehyd, known by the Handelsiiamen substances Ήοηοχ VSP "and Έσηοχ GL ^{1, 1} ', the two phenolic anti-oxidant agent 2246 and 425 (trade name of American Gyanamid Company); the product sold under the trade designation 703 by the ethyl Corporation substance ; 2,4,5-tri-hydroxybutyrophenoii and butylated hydroxytoluene.

To ensure their desired effect, the antioxidants must be present in a proportion of approx. 0.05 to approx. 2% by weight, based on the final weight of the polymer; within the more commercial A - ASPECTS of the present invention, but preferably in an amount of about 0.25 to about 0.5 G ew .- ^.

Examples of the third of the aforementioned additives are di-lauryl thiodipropionate, bi-stearyl thiodipropionate, a modified polymeric thioester, which is in an amount of. about 0.05 to about 2 percent _o -%, preferably about 1 O, up to 0.5 wt .. ct ^c / o, based on the final weight of the polymer is sufficient for the intended purpose. This special add-on

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substance is required as it is mutually reactive too the antioxidant and the polyolefin threads imparts heat resistance to the end product.

Heat stabilizers compatible with the polyolefin ^ and which also have good resistance to heat in the injection process can also be as described above Substance system can be added, provided that they ■ do not hike in the S'toff.

It has been proven that the polyolefin according to the invention manufactured objects are resistant to the fire flame. To do this, the following extended testing technique was used applied:

The object to be tested, for example a fabric, a film, etc. is held in a horizontal position and with this Object brought into direct contact with a flame. This state is maintained for a period of 5 seconds, which results in an ignition period of 5 seconds. When withdrawing the flame from direct contact with the The object must be each hammer produced on this during the previous ignition period in a time period of less go out by self-extinguishing for more than 2 seconds; this condition defines a useful value of fire resistance.

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16944

However, if it is a single thread, its Determined usefulness for the manufacture of 'fabrics is to be, then the ignition period is reduced to 2 and 3 seconds and the time it takes for the Flame is necessary after each ignition period.

To measure the quality of monofilaments, when the test described above was carried out to determine the average extinction time after an ignition period lasting 2 to 3 "seconds, the following rating system was established: on burning from 2 to 3 seconds, then the tested product is "excellent" with respect to its resistance to fire assessing degree issued when the flame at least 2 continues to burn up to a maximum of 5 seconds, the thread receives the judging level ^{"good:. l,} and when the flame at least If it continues to burn for 6 to a maximum of 10 seconds, the thread is then given the degree of fire resistance "sufficient"; Above 10 seconds, the evaluation grade "low" is given.

Does the thread have the degree of resistance to fire "excellent" , then it is sufficient if only the warp or only the weft threads are such threads in a fabric to give the fabric useful self-extinguishing properties;

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however, 'good' and 'when using loading the grade' must "Sufficient" both the warp and the weft threads from the fire-resistant threads according to the invention exist. A fabric whose warp and weft threads only have a "low" rating is not self-extinguishing. =

The invention is further illustrated by the following examples illustrates, in which all weight data, unless otherwise stated, in parts by weight, based on the Total weight. Particular advantages of the invention are described in detail by the examples. They serve primarily to illustrate the invention, but this does not make the invention in its generality and is not to be interpreted restrictively by the information contained in the following examples.

example 1

A monofHer polypropylene thread is made by adding of 13 parts, an organic bromophosphorus compound, 87 parts flaky polypropylene. Pie mix carefully for 10 to 15 seconds or more shaken, so that a practically homogeneous distribution

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is ensured and in the filler opening of a fuel injection line, which is equipped with a 4: 1 compression screw -, .- filled. The temperature of the screw area and that of the die is kept at 205 °. The möiiofilen Threads that were injected from this mixture are insofar of poor quality as they repeatedly "break and." shop fiber is clearly visible. When the injected Threads are stored for a longer period of time, excretion occurs.- Even with respect to the A test with regard to low-quality textile properties resulted the resistance to income the assessment degree 'good'.

Example 2

An ultraviolet light and weather resistant material system containing a dispersing agent which meets the requirements necessary for the present invention is made by mixing 3.7 parts di-lauryl thiodipropionate, 7 »4 parts Ional, 14.8 Parts of p-octylphenyl salicylate and 7 ^, 1 parts of the compound known under the trade name Arochlor 1260 prepared. This mixture is designated L-1 approach referred to as .. The mixture is heated to dissolve its solid components to 66 ⁰ G.

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13 ropes of this solution are added to 87 parts of flaky polypropylene, and after 10 to 15 seconds of shaking, the further procedure described in Example 1 is repeated with it have a ^{! I} low ^{; i} fire resistance.

Example J

According to the method described in Example 2, the L-1 batch is produced which contains the substances mentioned there which are resistant to ultraviolet light and weathering and, according to the invention, a dispersing agent. 10 parts of the L-1 approach in solution form are mixed with 5 parts of an organic Bromphosphorverbindung and the solution thus prepared is about 15 seconds long thoroughly mixed to 85 parts of "flake Polyprop3 ^ 1ens added ,, and the mixture f in the Einfüllöff- The sprayed monofilament threads are of good to excellent textile quality with no visible breaks or fibers. The results of the fire resistance test gave the grade of assessment for the monofilament threads "Good", there was no visible excretion on storage of the threads.

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A sample of this monofilament thread was made an equivalent of 6 "to 9 months exposed to the effects of sun and weather, the results were good with little noticeable damage to the filament from sunlight and general Weather influences occurred.

Example 4

7.5 parts of an organic bromophosphorus compound and 10 ropes of that known under the trade name Chlorowax "70" The fabric is mixed and flake into 82.5 parts Polypropylene added. This composition of matter will carefully mixed to ensure a homogeneous dispersion of its ingredients to achieve in each other. The mixture is then fed into the filling opening of a spray device and a monofilament thread according to that described in Example 1 Injection process produced. The spraying process goes well and results that can be used for textiles monofilament threads. The fire resistance of the monofilament threads was determined using the test procedure described above and as a result, the grade was found to be "good".

Example 5
A monofilament thread is made by combining

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0.5 parts of stearic acid with 10 parts of tris-2, i> -dibronio- · propyl phosphate and adding 89 »5 parts of polypropylene in Flockenfam. "This composition is mixed well to distribute the ingredients among each other, and it xcLrd an injection process according to Example 1 is connected to produce a monofilament thread that can be used for textiles. The spray went excellent, and so did the fire resistance test with the monofilament thread gave the rating "excellent".

Example 6

0.5 parts of double-pressed stearic acid and 10 parts of tris-2,3-dibromopropyl phosphate are mixed. The mixture is heated to 66 ° 0 to dissolve the stearic acid and then cooled to room temperature. The resulting paste becomes 83 »5 parts of flaky polypropylene added and in an IT vibratory mixer at slower speed Speed mixed for about 10 to 30 seconds until the paste is practically evenly distributed in the resin is. 6 parts of black pigment in lump form are added and mixing continues for several seconds continued, but only to the extent necessary to disperse the pigment. Excessive fooling would lead to wetting of the individual particles and so the irrigation flow properties of the synthetic resin mixture

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reduce. A good free-flowing load for however, the spraying device is desirable so that a uniform Spraying without interruption of the load by bridging in the filling opening of the spraying device is achieved.

The synthetic resin mixture is poured into the filling opening of a spray device with a 4: 1 compression screw. is equipped, filled. It is desirable that all parts are either chrome-plated or made of non-reactive metal in order to minimize reaction in the spray device. The temperatures in the area of the screw and in the matrix area were kept at 205 ° G.

Using a spray device with a heating mold opening from 1.1 mm, the synthetic resin is sprayed at a speed of 0.5 em / sec, in water to room temperature cooled and under infrared radiation at about 15> 0 ° C stretched in a ratio of 6: 1, so that a 0.34 mm thick thread is created, which has a tensile strength of about 4100 kg / cm. These threads are used as warp and weft threads to form an open-meshed fabric with one dimension of 50 x? 6 cm woven. The fabric made in this way is very difficult to ignite within an ignition time of 5 seconds, and xwhen ignition is reached,

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the flame goes out by itself within 2 seconds.

Example 7

23.1 parts of chlorinated biphenyl, 0.23 part double pressed Stearic acid and 7j7 parts of tris-2,3-dibromopropyl phosphate are mixed. The mixture is used to dissolve the pesticides as well as to distribute those contained in the mixture Shares heated to approximately 66 ° C. The mix-will then cooled to room temperature and about 68.1 parts of flaky polypropylene are added. The whole is mixed in a vibrating mixer at a slower speed. The: 'Mixing device is only used during operated for a time sufficient for the even distribution of the constituents, so that the free-flowing properties are abolished the resulting resin mixture is avoided.

The synthetic resin mixture is poured into the filling opening of a Given spray device and then carried out the spraying process under the conditions given in Example 6. The spraying process is possible without interference. The resulting threads were tested for their fire resistance tested and received the rating "good".

10 9816/20 39

Example

5 parts of chloric anhydride, ^ part of stearic acid and 10 parts of tris-2,3- <libromopropy! Phosphate are mixed and ^{heated to about 66 0} O to dissolve the solid constituents, then they are added to 79 parts of flaky polypropylene and the process subjected according to Example 6, 6 parts of a black dye being used; however, the resulting threads are not processed into a fabric.

The spraying goes well and the Seu <resistance text of the thread gives the grade "sufficient ^51" .

Example 9 '

84- parts of the one known under the trade name Arochlor 1260 Substance, 3 parts di-laurylthiodiproprionate, 3 parts lonal and 10 parts of 2-hydroxy-4-n-octoxylbenzophenol are mixed, to fight against destruction. Ultraviolet light and weather influences resistant fabric, hereinafter referred to as the L-4 approach.

3.6 parts of the above against ultraviolet light and

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Weather-resistant mixture of substances mixed with 10 parts of tris ^^ - ibromopropyl phosphate and then subjected to the process of Example 6, viobei 4 parts of a black dye concentrate and 82.4 Parts of flaky polypropylene are used. Of the The substance can be sprayed without interference. The emerging Threads were tested for their fire resistance and

received the rating "good". The sutures were further tested by the equivalent of 36 months Have been exposed to sunlight. The results were satisfactory, with only one readily acceptable little loss of physical properties occurred during this period.

Example 10

One part of stearic acid is mixed with 3 parts of tris-2,3-dibromopropyl phosphate mixed and heated to 66 C to dissolve the stearic acid, then cooled to room temperature, resulting in a paste that is 90 parts flaky Polypropylene is added. The resulting mixture is fed to a vibratory mixer and approximately Mix for 10 to 30 seconds, with 6 Parts of a black dye concentrate added will.

1Q9816 / 203S

This synthetic resin mixture is sprayed under the conditions described in Example 6 ". The spraying process proceeds well, but in the fire resistance test the threads only received the rating" low " ¹ .

• Example 11

The "method of Example 9 is used, with a deviation from this, 9-4 parts of the L-4 formulation, which protects against destruction by tri-violet light and the effects of the weather, are combined with 7 _J ^{Z |} parts tris-2,3-dibromopropyl phosphate" This mixture is in turn added to 83.2 inches of flaky polypropylene. No dye is added to the mixture.

The spraying process goes well. Testing of the threads on the jfeuiäerwiderstaiidsf BILITY gave the -Beur.teilun.gsgrad '' excellent '. The threads were trouble on Ultraviolettlichtzer- _Λ and tested the effects of the weather. Iiach, which it eight months the sun and the weather were about exposed they showed only an insignificant reduction caused by ultraviolet light irradiation and weather influences. *. their properties

Using the threads described above as weft threads

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and normal polypropylene threads as warp threads became one Fabric made and tested for fire resistance, being a useful Ifire resistance revealed.

Example 12

A film is made by pressing 0.5 parts twice Stearic acid mixed with a part of tris-2,3-dibromo propyl phosphate and added to dissolve the stearic acid of a real solution can be heated to approximately 66 ° C. After cooling down to room temperature, a paste is formed that is 98.5 parts of flaky polypropylene in a rocking mixer is mixed. The mixing time is limited to a maximum of 30 seconds to ensure that the individual particles are wetted is prevented, since otherwise the free-flowing properties of the mixture of substances were essentially reduced.

The mixture is poured into the filling opening of a spray device, which is equipped with a 15 cm gap matrix. The product ejected from the die becomes Chilled on a water-cooled chrome-plated roller. the The temperature of the compression screw and the die is kept at 205 ° G.

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There were no difficulties in spraying a 0.18mm thick film after an ignition period lasting 5 seconds clears itself within 1 to 4 seconds.

Example 13

Pressed films can be very easily cut into pieces from one piece Produce a mixture of substances. To do this, 0.5 parts are initially required double-pressed stearic acid with 10 parts of tris-2,3-dibromopropy! phosphate mixed, this mixture '' is used to dissolve the stearic acid to a clear solution to 66 G heated. After cooling to about room temperature (27 G), a paste is formed which, with 85 »5 parts, is flaky Polypropylene and 6 parts of a black lumpy dye off concentrate s mixed in a vibratory mixer will. The mixing time is limited to 10 to 30 seconds to avoid wetting of the individual particles, wocLuiich the free-flowing properties of the resulting mixture of substances would be significantly reduced.

The synthetic resin produced in this way is poured into the filling opening introduced a spray device, and there are threads of at least 1.1 mm in diameter die temperature Die is kept at 205 ° 0 during the injection process

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Injected threads are not stretched, but in the received one Cut the shape into pieces about 13 mm long. This chunky st off composition is used to make films to press. It can also turn into other objects or shapes be pressed.

Films can be produced from the lumpy material composition in a simple manner by pressing, in

■ - to which a lot of this material is placed between two pieces of Teflon-coated fiberglass as a mounting fabric and the whole thing between the pressure stamps of a press. The film is produced at a stamp pressure of 4-300 kg and a temperature of approx. 190 °, with spacers being used to set the desired film thickness. After a pressing time of 10 to 30 seconds, the rams are opened and the film that is still between • the pulling fabric is removed and cooled; after cooling down, the mounting fabric is removed »

The produced film obtained in the fire resistance test; the grade "good", where or during 5 Seconds has been exposed to an open flame. At a such [remainder extinguished 0.2 and 0.6 mm thick and 1 $ mm wide films of this type by themselves in less than 3 seconds.

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. Example 14

A monofilament thread is made by first inserting in a swing device to 82.5 parts floe-shaped Polypropylene 10 parts of a powdery substance known under the trade name Chlorowax 70 were added will. After several minutes of careful mixing, 7-5 parts of tris-2,> -dibromopropyl phosphate, heated to about 66 ° G, are obtained added. Mixing will continue for a maximum of 30 seconds. These Limitation is useful, so that the individual particles are wetted and the flow properties are reduced as a result the mixture is avoided.

The synthetic resin mixture is poured into the filling opening of a Introduced spray device and load in monofilament useful for textiles according to the in Example 6, described Procedure injected.

The threads produced in this way were of good textile quality and 'were rated "excellent" in the fire resistance test.

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Claims (1)

Claims ..IPeuerwi the stable polyolefin made from a polyolefin compound exists, which is mixed with an organic bromine compound, g e k e η η ζ e i c h η e t through a dispersing agent for the organic bromine compound to disperse them substantially uniformly within the polyolefin. 2. Polyolefin according to claim 1 in film form, characterized by a content of organic bromine compound of approx. 1 to approx. 8% and of dispersing agent of approx. 0.05 'to approx. 20 %. 3. Polyolefin according to claim 1 as in a predetermined form formed object, characterized by an essentially uniformly dispersed in the polyolefin Proportion of approx. 1 to approx. 8% by weight of organic bromine 109816/2039 TELEPHONE: 018 4057 compound and approx. 0.05 to approx. 20 wt. yö of dispersing Means for the bromine compound. 4-. Polyolefin according to claim 3, characterized in that that the dispersing IHttel at least one about . chlo- 'containing from approx. 20 to approx. 70% by weight of chlorine contains rated polyphenyl compound. 5. Polyolefin according to claim 5 »characterized by a organic bromine phosphate as an organic bromine compound. 6. Polyolefin as trained in a predetermined EOrm Object according to claim? » marked by a tris-2,3-dibromopropy! phosphate or another organic phosphorus bromine compound as organic Bromine compound. 7 · Polyolefin according to claim 1 as an object constructed in a predetermined shape, characterized by a proportion of approximately 1 to approximately 12% by weight of an organic bromine compound and from approximately 0.05 to approximately 20% by weight of a dispensing agent for the organic bromine compound and from approx. 0.1 to approx. 9% by weight of predetermined against ultraviolet light 109816/2039 St. and weathering stabilizing the polyolefin Providing increased resistance to destruction by ultraviolet light and the effects of the weather Fabrics. 8. Polyolefin according to claim. 7 »characterized by a proportion of approx. 0.05" to approx. 4 % stearic acid and from approx. 0 to approx. 16 % of at least one chlorinated poly containing approx. 20 to approx. 70% by weight of oil 'phenyl compound in the dispersing agent.' 9 · polyolefin according to claim 7 »characterized in that the predetermined substances stabilizing against ultraviolet light · and weathering influences a) from approx. 0 to 5 ³ / ° of an ultraviolet * absorber compatible with the polyolefin, b) from approx. 0.05% to approx. 2% by weight of one with the polyolefin compatible anti-oxidizing agent and-c) from 0.05 % to about 2 % of one together with the antioxidant reactive (synergistically reactive) and a compound imparting heat stability to the polyolefin. 10. Polyolefin according to claim 9 »characterized by a Polypropylene as a polyolefin compound. 109816/2039 Hi 11. Polyolefin according to claim 10, characterized by Thread shape. 12. Polyolefin according to claim 9? characterized in that which the polyolefin for the chain and / or / weft threads of a Fabric is used. 13 «A polyolefin according to claim 1 in yarn form or as otherwise formed in a predetermined shape article characterized by substantially uniformly dispersed from about 4 to about 8% of an organic Bromphosphates, of about 5 about his / o 10 ° of he disp greedy coat for the bromophosphate and from about 0.1 to about 9 wt .-% of predetermined, the polyolefin an increased resistance to destruction by ultraviolet light and weathering imparting stabilizers containing polypropylene. . A polyolefin according to claim 13, characterized in that the dispersing agent from about 1 to about '4 ° / o stearic acid, and from about 9 l> is about 6% of a about 20 to about .70 wt .-% Chlorine-containing substance from the group of chlorinated polyphenyl compounds. 15 · polyolefin according to claim 1 in film form, characterized through polypropylene, in which evenly dispersed at least about 1 wt. an organic bromine compound 10 98 16/2039 - * -: '' 16944U HH and about 0.05 % to about 20% by weight of a dispersing agent for the bromine compound and about 0.1 to about 9% by weight of selected stabilizers which give the polyolefin increased resistance to destruction by ultraviolet light and weathering included are _o 16. A method for spraying a fire-resistant polyolefin compound according to claim 1, 11, 13 or 14 " in thread form, characterized by the following process steps: a) mixing about 3 to about 12 wt .-% of an organic bromine compound and about 0.05 to about 20 wt .-% of a dispergiereiiden agent for the bromine compound with about 97 _o to about 68% of a polyolefin resin, and b) Filling the mixture into a spray device and Spritzi
approx. 24-5 ⁰ C. and spraying at a temperature from approx. 175 ° ö 17 · Method of spraying a fire resistant egg as well as polyolefin resistant to ultraviolet light and weathering according to claim 7 in I? adenform, characterized by the following process steps: 10 9816/203 9 HS a) Mixes of approx. 0.05 % "to approx. 20% by weight of a dispersing agent and from approx. 0.1%" to approx. 9 % by weight of approx. 0 "to approx. 5% by weight .-% UltravicLettlichtabsorbers containing material compatible with the polyolefin compound and approx. 0.05% Ms approx. 2% by weight of an antioxidant material compatible with the polyolefin compound and approx. 0.05 % to approx. 2% by weight of a heat absorber, b) heating the mixture to approx. 65 ° G to dissolve the solid constituents it contains, c) adding the mixture to a mixture of substances consisting of about 3% to about 12% by weight of an organic bromine compound and about 96.8 % to about 59% by weight of a polyolefin compound. d) mixing, ' e) spraying at a! temperature from about 175 ° G to about 24 · 5 ^Ο 0 for producing a synthetic textile yarn. 18 .. The method of claim 17, wherein the polyolefin is at least 1 wt - o at disp it contains ° / gierendem means. 109816/2039 cUdursh, as the injected threads are cut into pieces in lengthwise section 3 and these are pressed onto films or into irorbestiiaaitep ? ozm objects. f BAD ORIGINAL 199916/2099