Flame-retardant polymer compositions

Abstract

Flame-retardant polymer compositions contain a flame-retardant system consisting of a phosphorus/nitrogen-component, aluminum hydroxide, and a least one synergetically active component selected from the group consisting of organic nitrogen compounds, polyalcohols or derivatives thereof, the phosphorus/nitrogen-component being ammonium polyphosphate, if desired.

Description

This invention relates to flame-retardant polymer compositions, preferably duroplastic polymer compositions and more preferably to unsaturated polyester resins.

It is known that flame-retardant properties can be imparted to unsaturated polyester resins by admixing these resins either with an inorganic flame-retardant agent, such as aluminum hydroxide, or organic flame-retardant agent, such as a chloroparaffin or a halogenated biphenyl, or by chemically modifying the acid or alcohol component of the unsaturated monomer, commonly by halogenation. In the event of the unsaturated polyester being one containing halogen, the polyester is frequently admixed additionally with antimony trioxide acting as a synergist (cf. "Handbook of Plastics Flammability and Combustion Toxicology", Noyes Publications, Park Ridge, N.J., U.S.A. (1983)).

In U.S. Pat. No. 3,810,862, it has been disclosed that flame-retardant properties can be imparted to polyolefins using a mixture of ammonium polyphosphate, melamine and dipentaerythritol or of melamine pyrophosphate and dipentaerythritol.

Flame-retardant systems based on ammonium polyphosphate, melamine and polyamide 6 have been disclosed in U.S. Pat. No. 4,198,493, and further systems of this kind based on ammonium polyphosphate, melamine and tris-2-hydroxyethylisocyanurate or ammonium polyphosphate, pentaerythritol or tripentaerythritol and tris-2-hydroxyethyl-isocyanurate, and also ammonium polyphosphate, cyanuric acid and tris-2-hydroxyethyl-isocyanurate have been disclosed in U.S. Pat. No. 4,198,493.

Still further compositions based on ammonium polyphosphate, melamine-cyanurate and hydroxyalkyl esters of isocyanuric acid have been suggested in EP-PS No. 204 027 for imparting flame-retardant properties to polyolefins.

Although aluminum hydroxide used separately and combinations of ammonium polyphosphate with a synergetically active compound were found to have no effective flame-retardant activity for unsaturated polyesters, we have now unexpectedly discovered that the combination of aluminum hydroxide with ammonium polyphosphate and various synergetically active substances is a highly effective flame-retardant system for unsaturated polyesters.

The term unsaturated polyester resin (UP-resins) is used herein to denote those products which are obtainable by means of a condensation reaction from saturated or unsaturated dicarboxylic acids or their anhydrides and a diol. The dicarboxylic acids most useful for this purpose are maleic acid, which is commonly used in the form of its anhydride, and fumaric acid. Propane diol-1,2 is the representative customarily selected from the diol series. Styrene which is miscible with a polyester resin in whatever ratio and is easy to copolymerize, is the reactive monomer most frequently used. Unsaturated polyester resins normally contain between 30 and 40 weight % of styrene (cf. Ullmanns Encyklopadie der technischen Chemie, volume 19, pages 79-88, Verlag Chemie, Weinheim, (1980)).

The present invention relates more particularly to a flame-retardant polymer composition which is characterized in that it contains a flame-retardant system consisting essentially of a phosphorus/nitrogen-component, aluminum hydroxide, and at least one synergetically active component selected from the group consisting of organic nitrogen compounds, polyalcohols or derivatives thereof.

Further preferred and separate features typical of the flame-retardant polymer compositions of this invention provide:

(a) for the flame-retardant polymer composition to contain, as the phosphorus/nitrogen-component, 5-45 parts by weight of ammonium polyphosphate per 100 parts by weight of polymer;

(b) for the said ammonium polyphosphate to contain 0.5-25 weight % of a water-insoluble artificial, preferably cured, resin encapsulating the individual ammonium polyphosphate particles;

(c) for the said ammonium polyphosphate to contain 0.5-25 weight % of a reaction product of a polyisocyanate with a carbodiimidization catalyst, the polycarbodiimide formed encapsulating the individual ammonium polyphosphate particles;

(d) for the said ammonium polyphosphate to contain 0.5-25 weight % of a reaction product of a polyisocyanate and a polyhydroxy compound, the polyurethane formed encapsulating the individual ammonium polyphosphate particles;

(e) for the said ammonium polyphosphate to contain 0.5-25 weight % of a reaction product of a polyisocyanate with a trimerization catalyst, the polyisocyanurate formed encapsulating the individual ammonium polyphosphate particles;

(f) for the said ammonium polyphosphate to contain 0.5-25 weight % of a reaction product of a polyisocyanate and water, the polyurea formed encapsulating the individual ammonium polyphosphate particles;

(g) for the said ammonium polyphosphate to contain 0.5-25 weight % of a cured melamine/formaldehyde-resin, the melamine/formaldehyde resin encapsulating the individual ammonium polyphosphate particles;

(h) for the said ammonium polyphosphate to contain 0.5-25 weight % of a cured epoxide resin, the epoxide resin encapsulating the individual ammonium polyphosphate particles;

(i) for the organic nitrogen compound used to be melamine and/or a melamine derivative;

(j) for the organic nitrogen compound used to be cyanuric acid or isocyanuric acid and/or a derivative of these acids;

(k) for the organic nitrogen compound used to be a condensation product of ethylene, urea and formaldehyde;

(l) for the polyalcohol used to be pentaerythritol and/or a derivative thereof;

(m) for the polyalcohol used to be dipentaerythritol and/or a derivative thereof;

(n) for the flame-retardant polymer composition to contain 1 to 25 parts by weight of the synergetically active component per 100 parts by weight of polymer;

(o) for the said flame-retardant polymer composition to contain 50-175 parts by weight of aluminum hydroxide per 100 parts by weight of polymer;

(p) for the said flame-retardant polymer composition to contain the said ammonium polyphosphate and said synergetically active component in a ratio by weight of 1:1 to 10:1;

(q) for the said flame-retardant composition to contain the said aluminum hydroxide and said combination of ammonium polyphosphate and synergetically active component in a ratio by weight of 1:1 to 15:1;

(r) for the said flame-retardant polymer composition to be a duroplastic;

(s) for the said flame-retardant polymer composition to be an unsaturated polyester;

(t) for the said flame-retardant polymer composition to be reinforced by means of glass fibers.

The aluminum hydroxide should conveniently be used in the form of those products which have been disclosed in U.S. Pat. Nos. 4,340,579 and 4,421,876, respectively.

The ammonium polyphosphate which should preferably be used is a free-flowing, pulverulent, scarcely water-soluble ammonium polyphosphate of the formula (NH.sub.4 PO.sub.3).sub.n, where n is a number between 20 and 1000, especially 500 and 1000; it should preferably be used in the form of particles of which more than 99% have a size of less than 45 .mu.m.

The following Examples and Tables illustrate the invention in greater detail which however is naturally not limited thereto. The parts are by weight unless otherwise stated.

EXAMPLE 1

1. Preparation of Blend of Polyester/Flame-Retardant Agent

100 parts.RTM. ALPOLIT UP 002 (a registered Trade Mark of Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany)--it is a slightly viscous, highly reactive unsaturated polyester resin dissolved in styrene.

100 parts.RTM. APYRAL 2 (a registered Trade Mark of VAW; Vereinigte Aluminium Werke AG, Bonn, Federal Republic of Germany)--it is an aluminum hydroxide originating from the BAYER-process and modified by the process disclosed in EP-PS No. 11 667 (=U.S. Pat. Nos. 4,340,579, 4,421,876).

0.3 part cobalt accelerator NL 49 P (a product of Akzo Chemie GmbH, Duren, Federal Republic of Germany)--it is a cobalt octoate solution in dibutylphthalate containing 1 weight % cobalt.

were mixed in a suitable container using a dissolver disc.

Next,

2.0 parts butanox M 50 (a product of Akzo Chemie GmbH, Duren)--it is methylethylketone peroxide desensitized with dimethyl phthalate, and available as a clear, colorless liquid containing at least 9 weight % active oxygen--and the whole is mixed once again.

2. Preparation of UP-Resin Laminates

Approximately 50% of the blend of polyester/flame-retardant agent was regularly distributed on a parting film (.RTM.HOSTAPHAN RN 100/0.1 mm thick, a registered Trade Mark of Hoechst Aktiengesellschaft). Next, a matched, styrene-insoluble textile glass mat having a surface weight of 450 g/m.sup.2 was placed thereon. By means of a lambskin roller, the second 50% portion of the blend of polyester/flame-retardant agent was regularly distributed on the glass mat and the occluded air was expelled. The laminate was then covered with a further parting film.

3. Preparation of Test Plate

The laminate was given into a warm water-heated BECKER-VAN HULLEN press and molded at a temperature of 50.degree. C., under a pressure of 10 bars and over a period of about 1 hour into a test plate 1.6 mm thick.

4. Flammability Tests

4.1 The flammability of the composition was tested in accordance with the Underwriters Laboratories procedure "Test of Flammability of Plastic Material"-UL 94 dated as of May 2, 1975, on specimens 127 mm long, 12.7 mm wide and 1.6 mm thick.

4.2 The oxygen index was determined in a modified apparatus substantially in accordance with ASTM-D 2863-74

The results of the flammability tests are reported in Table 1.

EXAMPLES 2-62

The test plates were made and tested as described in Example 1. The data indicated in Tables 1-12, columns 2 and 3 relate to flame-retardant agents different in nature and concentration from those used in Example 1.

In addition to this, the following products were used in Examples 2-62.

.RTM.EXOLIT 422 (a registered Trade Mark of Hoechst Aktiengesellschaft)--it is a fine particulate, scarcely water-soluble ammonium polyphosphate of the formula (NH.sub.4 PO.sub.3).sub.n, where n is about 700; more than 99% of the ammonium polyphosphate particles have a size of less than 45 .mu.m.

.RTM.EXOLIT 462 (a registered Trade Mark of Hoechst Aktiengesellschaft)--it is a microencapsulated ammonium polyphosphate obtained by the process disclosed in EP-B-0 180 795, containing about 10 weight % encapsulating material consisting of a cured melamine/formaldehyde resin.

.RTM.EXOLIT 455 (a registered Trade Mark of Hoechst Aktiengesellschaft)--it is a microencapsulated ammonium polyphosphate obtained by the process disclosed in U.S. Pat. No. 4,514,328, containing about 10 weight % encapsulating material consisting of an epoxide resin.

.RTM.EXOLIT 470 (a registered Trade Mark of Hoechst Aktiengesellschaft)--it is a microencapsulated ammonium polyphosphate obtained by the process disclosed in DE-OS No. 35 26 006, containing about 10% encapsulating material consisting of the reaction product of a polyisocyanate with a carbodiimidization catalyst.

.RTM.SPINFLAM MF 80 (a registered Trade Mark of Montefluos, Milano, Italy)--it is a condensation product of ethylene urea and formaldehyde, containing 28% nitrogen.

As can be inferred from Tables 1-5, neither aluminum hydroxide nor a combination of ammonium polyphosphate with a synergetically active component permit an unsaturated polyester which has been treated therewith to be classified in any of UL 94-classes V-2 to V-0.

In clear contrast with this, it is evident from Tables 6-12 that even minor quantities of the various ammonium polyphosphates used in combination with the synergetically active component and aluminum hydroxide unexpectedly permit the UL 94-classes V-1 and V-0 to be reliably obtained.

TABLE 1______________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74 Flame-retardant System Total Quantity quantity UL-94-Compar. parts/100 parts/100 vertical OxygenExamples Material parts UP.sup.2 parts UP.sup.2 test Index______________________________________1 APYRAL 100 100 n.c..sup.3 0.30 22 APYRAL 125 125 n.c. 0.32 23 APYRAL 150 150 n.c. 0.33 24 APYRAL 175 175 n.c. 0.36 2______________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 n.c. = not classified as V0, V1 or V2 TABLE 2__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74 Flame-retardant System UL-94-Compar. Quantity Total quantity vertical OxygenExamples Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________5 EXOLIT 422 15 25 n.c..sup.3 0.24 Melamine 5 Pentaaerythritol 56 EXOLIT 462 15 25 n.c. 0.23 Melamine 5 Pentaaerythritol 57 EXOLIT 422 22.5 37.5 n.c. 0.25 Melamine 7.5 Pentaaerythritol 7.58 EXOLIT 462 22.5 37.5 n.c. 0.25 Melamine 7.5 Pentaaerythritol 7.59 EXOLIT 422 30 50 n.c. 0.26 Melamine 10 Pentaaerythritol 1010 EXOLIT 462 30 50 n.c. 0.26 Melamine 10 Pentaaerythritol 1011 EXOLIT 422 45 75 V-0 0.29 Melamine 15 Pentaaerythritol 1512 EXOLIT 462 45 75 V-0 0.35 Melamine 15 Pentaaerythritol 15__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM. ALPOLIT UP 002; .sup.3 n.c. = not classified as V0, V1 or V2 TABLE 3__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74 Flame-retardant System UL-94-Compar. Quantity Total quantity vertical OxygenExamples Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________13 EXOLIT 422 25 50 n.c..sup.3 0.25 Spinflam 25 MF 8014 EXOLIT 422 37.5 50 n.c. 0.25 Spinflam 12.5 MF 8015 EXOLIT 462 25 50 n.c. 0.;24 Spinflam 25 MF 8016 EXOLIT 462 37.5 50 n.c. 0.25 Spinflam 12.5 MF 8017 EXOLIT 422 50 75 n.c..sup.3 0.29 Spinflam 25 MF 8018 EXOLIT 422 60 75 n.c. 0.30 Spinflam 15 MF 8019 EXOLIT 462 50 75 n.c. 0.31 Spinflam 25 MF 8020 EXOLIT 462 60 75 n.c. 0.33 Spinflam 15 MF 80__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 n.c. = not classified as V0, V1 or V2 TABLE 4__________________________________________________________________________Flammability Test in Accordance with UL-94-vetical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74 Flame-retardant System UL-94-Compar. Quantity Total quantity vertical OxygenExamples Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________21 EXOLIT 422 25 50 n.c..sup.3 0.25 THEIC.sup.4 2522 EXOLIT 422 37.5 50 n.c. 0.27 THEIC 12.523 EXOLIT 462 25 50 n.c. 0.25 THEIC 2524 EXOLIT 455 25 50 n.c. 0.26 THEIC 2525 EXOLIT 455 37.5 50 n.c..sup.3 0.27 THEIC.sup.4 12.526 EXOLIT 470 25 50 n.c. 0.28 THEIC 2527 EXOLIT 470 37.5 50 n.c. 0.28 THEIC 12.5__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 n.c. = not classified as V0, V1 or V2 .sup.4 THEIC = tris(2-hydroxyethyl)-isocyanurate TABLE 5__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74 Flame-retardant System UL-94-Compar. Quantity Total quantity vertical OxygenExamples Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________28 EXOLIT 422 37.5 50 n.c..sup.3 0.24 MCY.sup.5 12.529 EXOLIT 422 37.5 50 n.c. 0.26 DIPIT.sup.6 12.530 EXOLIT 422 30 50 n.c. 0.26 THEIC.sup.4 10 DIPIT 1031 EXOLIT 422 30 50 n.c. 0.26 MCY 10 DIPIT 1032 EXOLIT 422 33 50 n.c..sup.3 0.25 MCY.sup.5 10 THEIC.sup.4 1033 EXOLIT 462 30 50 n.c. 0.26 MCY 10 THEIC 1034 EXOLIT 455 30 50 n.c. 0.27 MCY 10 THEIC 1035 EXOLIT 470 30 50 n.c. 0.28 MCY 10 THEIC 10__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 n.c. = not classified as V0, V1 or V2 .sup.4 THEIC = tris(2-hydroxyethyl)-isocyanurate .sup.5 melamine cyanurate .sup.6 DIPIT = dipentaerythritol TABLE 6__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74Examples Flame-retardant System UL-94-of inven- Quantity Total quantityu vertical Oxygention Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________36 EXOLIT 422 30 100 V-1 0.36 Melamine 10 Pentaaerythritol 10 APYRAL 2 5037 EXOLIT 422 36 100 V-0 0.37 Melamine 7 Pentaaerythritol 7 APYRAL 2 5038 EXOLIT 422 15 150 V-1 0.39 Melamine 5 Pentaerythritol 5 APYRAL 2 12539 EXOLIT 462 15 150 V-1 0.40 melamine 5 Pentarythritol 5 APYRAL 2 12540 EXOLIT 455 15 150 V-0 0.39 Melamine 5 Pentarythritol 5 APYRAL 2 12541 EXOLIT 470 15 150 V-1 0.39 Melamine 5 Pentaerythritol 5 APYRAL 2 125__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM. ALPOLIT UP 002; TABLE 7__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74Examples Flame-retardant System UL-94-of inven- Quantity Total quantity vertical Oxygention Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________42 EXOLIT 462 37.5 100 V-1 0.30 MF 80 12.5 APYRAL 2 5043 EXOLIT 462 37.5 150 V-0 0.38 MF 80 12.5 APYRAL 2 10044 EXOLIT 455 20 175 V-0 0.45 MF 80 5 APYRAL 2 15045 EXOLIT 455 16 170 V-0 0.43 MF 80 4 APYRAL 150__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 MF 80 = .RTM.Spinflam MF 80 TABLE 8__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74Examples Flame-retardant System UL-94-of inven- Quantity Total quantity vertical Oxygention Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________46 EXOLIT 462 40 150 V-0 0.38 THEIC.sup.3 10 APYRAL 2 10047 EXOLIT 462 20 150 V-0 0.36 THEIC 5 APYRAL 2 12548 EXOLIT 462 12 165 V-0 0.41 THEIC 3 APYRAL 2 15049 EXOLIT 462 8 160 V-1 0.39 THEIC 2 APYRAL 2 150__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 THEIC = tris(2-hydroxyethyl)-isocyanurate TABLE 9__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74Examples Flame-retardant System UL-94- .of inven- Quantity Total quantity vertical Oxygention Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________50 EXOLIT 462 20 175 V-0 0.41 MCY.sup.3 5 APYRAL 2 15051 EXOLIT 462 16 170 V-0 0.37 MCY 4 APYRAL 2 15052 EXOLIT 462 12 165 V-1 0.36 MCY 3 APYRAL 2 150__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 MCY = melamine cyanurate TABLE 10__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74Examples Flame-retardant System UL-94-of inven- Quantity Total quantity vertical Oxygention Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________53 EXOLIT 470 20 175 V-0 0.44 DIPIT.sup.3 5 APYRAL 2 15054 EXOLIT 470 16 170 V-0 0.42 DIPIT 4 APYRAL 2 15055 EXOLIT 470 12 165 V-1 0.41 DIPIT 3 APYRAL 2 150__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 DIPIT = dipentaerythritol TABLE 11__________________________________________________________________________Flammability Test in Accordance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74Examples Flame-retardant System UL-94-of inven- Quantity Total quantity vertical Oxygention Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________56 EXOLIT 422 15 150 V-0 0.38 THEIC.sup.3 5 DIPIT.sup.4 5 APYRAL 12557 EXOLIT 470 15 150 V-0 0.40 THEIC 5 DIPIT 5 APYRAL 2 12558 EXOLIT 462 15 150 V-0 0.37 MCY.sup.5 5 DIPIT 5 APYRAL 2 12559 EXOLIT 470 15 150 V-0 0.38 MCY 5 DIPIT 5 APYRAL 2 125__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 THEIC = tris(2-hydroxyethyl)-isocyanurate .sup.4 DIPIT = dipentaerythritol .sup.5 MCY = melamine cyanurate TABLE 12__________________________________________________________________________Flammability Test in Accoedance with UL-94-vertical test.sup.1Oxygen Index in Accordance with ASTM-D 2863-74Examples Flame-retardant System UL-94-of inven- Quantity Total quantity vertical Oxygention Material parts/100 parts UP.sup.2 parts/100 parts UP.sup.2 test Index__________________________________________________________________________60 EXOLIT 462 30 150 V-0 0.35 MCY.sup.3 10 THEIC.sup.4 10 APYRAL 2 10061 EXOLIT 462 15 150 V-0 0.37 MCY 5 THEIC 5 APYRAL 2 12562 EXOLIT 462 12 170 V-0 0.40 MCY 4 THEIC 4 APYRAL 2 150__________________________________________________________________________ .sup.1 Underwriters Laboratories "Test for Flammability of Plastic MaterialUL 94" specimens: 127 mm long, 12.7 mm wide and 1.6 mm thick .sup.2 UP = .RTM.ALPOLIT UP 002; .sup.3 MCY = melamine cyanurate .sup.4 THEIC = tris(2-hydroxyethyl)-isocyanurate

Claims

1. A flame-retardant unsaturated polyester resin composition, containing a flame-retardant system comprised of 5 to 45 parts by weight ammonium polyphosphate per 100 parts by weight polymer, 50 to 175 parts by weight of aluminum hydroxide per 100 parts by weight polymer and at least 1 to 25 parts by weight of a synergetically active component selected from the group consisting of organic nitrogen compounds, polyalcohols, derivatives of polyalcohols and combinations of said synergetically active components per 100 parts by weight of polymer; said ammonium polyphosphate containing 0.5 to 25 weight % of a water-insoluble synthetic resin encapsulating the individual ammonium polyphosphate particles; said organic nitrogen compounds being selected from the group consisting of melamine, cyanuric acid, isocyanuric acid and derivatives thereof and a condensation product of ethylene, urea and formaldehyde; said polyalcohol being selected from the group consisting of pentaerythritol, dipentaerythritol and derivatives thereof; and said aluminum hydroxide and the combination of ammonium polyphosphate and synergetically active component being contained in a ratio by weight of 1:1 to 15:1.

2. A flame-retardant polymer composition as claimed in claim 1, containing the said ammonium polyphosphate and said synergetically active component in a ratio by weight of 1:1 to 10:1.

3. A flame-retardant polymer composition as claimed in claim 1, wherein the said polymer is a polymer reinforced by glass fibres.

4. A flame-retardant polymer composition as claimed in claim 1, wherein the said water-insoluble synthetic resin is cured.

5. A flame retardant polymer composition as claimed in claim 1, wherein said ammonium polyphosphate has been encapsulated by a polycarbodiimide formed by reaction of a polyisocyanate with a carbodiimidization catalyst.

6. A flame retardant polymer composition as claimed in claim 1, wherein said ammonium polyphosphate has been encapsulated by a polyurethane formed by reaction of a polyisocyanate and a polyhydroxy compound.

7. A flame-retardant polymer composition as claimed in claim 1, wherein said ammonium polyphosphate has been encapsulated by a polyisocyanurate formed by reaction of a polyisocyanate with a trimerization catalyst.

8. A flame-retardant polymer composition as claimed in claim 1, wherein said ammonium polyphosphate has been encapsulated by a polyurea formed by reaction of a polyisocyanate and water.

9. A flame-retardant polymer composition as claimed in claim 1, wherein said ammonium polyphosphate has been encapsulated by a cured melamine/formaldehyde-resin.

10. A flame-retardant polymer composition as claimed in claim 1, wherein said ammonium polyphosphate has been encapsulated by a cured epoxide resin.

11. A flame-retardant unsaturated polyester resin, containing a flame-retardant system comprised of 8 to 40 parts by weight ammonium polyphosphate per 100 parts by weight polymer, 50 to 150 parts by weight of aluminum hydroxide per 100 parts by weight polymer and at least 2 to 20 parts by weight of a synergetically active component selected from the group consisting of organic nitrogen compounds, polyalcohols, derivatives of polyalcohols and combinations of said synergetically active components per 100 parts by weight polymer; said ammonium polyphosphate containing 0.5 to 25 weight % of a water-insoluble synthetic resin encapsulating the individual ammonium polyphosphate particles; said organic nitrogen compounds being selected from the group consisting of melamine, cyanuric acid, isocyanuric acid and derivatives thereof and a condensation product of ethylene, urea and formaldehyde; said polyalcohol being selected from the group consisting of pentaerythritol, dipentaerythritol and derivatives thereof; and said aluminum hydroxide and the combination of ammonium polyphosphate and synergetically active component being contained in a ratio by weight of 1:1 to 15:1.

12. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said ammonium polyphosphate has been encapsulated by a polycarbodiimide formed by reaction of a polyisocyanate with a carbodiimidization catalyst.

13. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said ammonium polyphosphate has been encapsulated by a polyurethane formed by reaction of a polyisocyanate and a polyhydroxy compound.

14. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said ammonium polyphosphate has been encapsulated by a polyisocyanurate formed by reaction of a polyisocyanate with a trimerization catalyst.

15. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said ammonium polyphosphate has been encapsulated by a polyurea formed by reaction of a polyisocyanate and water.

16. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said ammonium polyphosphate has been encapsulated by a cured melamine/formaldehyde-resin.

17. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said ammonium polyphosphate has been encapsulated by a cured epoxide resin.

18. A flame-retardant unsaturated polyester resin as claimed in claim 11, containing said ammonium polyphosphate and said synergetically active component in a ratio by weight of 1:1 to 10:1.

19. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said polymer is a polymer reinforced by glass fibres.

20. A flame-retardant unsaturated polyester resin as claimed in claim 11, wherein said water-insoluble synthetic resin is cured.