DE1771844A1 - Fire-retardant compositions and plastics containing them and articles made therefrom - Google Patents

Description

PATENT LAWYERS " DIPL-CHEM. DR. WERNER KOCH DR.-ING. RICHARD GLAWE DIPL-ING. KLAUS DELFS DIPL-PHYS. DR. WALTER MOLL HAMBURG MDNCHEN 1771844

2000 Hamburg 52 ■ WaHxjlraB. 12 · Ruf (92255 8000 MOnch.n 22 · LlabhtrntraS · 20 · «uf 22ί54ί

L J

YOUR SIGN YOUR MESSAGE FROM OUR SIGN MONKS

A 95

REGARDS: '

BAKELITE XYLONITE LIMITED

27 Blandford Street,
London WI, England

Fire-retardant composition and plastics containing them and articles made therefrom.

■ λ * - ···· ■ · ■ - <,. The invention relates to fire retardant compositions

and products containing them. In particular, the invention relates to fire retardant compositions that are particularly useful are included for use with synthetic resins

109886/0486

the production of laminates with improved fire retardant and non-flammable properties.

Laminates have been known to exist for many years made of fillers treated with heat and pressure and bonded to one another, as well as synthetic resins in the form of varnishes. In most cases the fillers are of a fibrous nature, e.g. paper, cotton, rayon, or asbestos Glass. The synthetic resins are generally thermosetting resins, such as epoxy or polyester resins, urea-formaldehyde condensation products, Melamine-formaldehyde condensation products or condensation products of Phenolic compounds and aldehydes (phenolic aldehyde resins). These reinforced materials are widely used in Form of decorative laminates made, usually a core of several layered paper webs have, which are impregnated with a thermosetting resin, for example a phenolic resin, as well as a or several cover layers made of paper, which are impregnated with a melamine resin and have a decorative structure. Furthermore, such reinforced materials are widely manufactured for electrical applications and in this case often have a conductive surface layer, for example a copper foil,

- 2 -

109886/0486

so that the metallic surface of this layer is partially etched and printed circuits are thereby produced can.

Laminates of this and other types are manufactured on a large scale for a wide range of uses been used. In recent years, the demands placed on the properties of these laminates have increased become stricter. In this context it has become more and more important for many purposes, to improve the fire-retardant properties and the non-flammability of the laminates. this will usually achieved by adding a suitable fire retardant agent. Numerous fabrics are made for this purpose has been proposed. In many cases, however, the fire retardant additive improves the fire retardant properties and non-flammability, but it adversely affects other desirable properties such as e.g. on the dielectric constant, the power factor, the water absorption and the punching properties, i.e. properties, which are particularly important in laminates for electrical purposes. For these and similar reasons there is a need for a fire retardant additive that has the fire retardant properties and the non-

103886/0486

Flammability of the laminates improved, but none or only very slight adverse properties on other important properties for the respective application Has properties. The present invention therefore aims to provide fire retardant compositions, which, when added to a laminate, take this need into account better than previously known compositions.

Fire retardant composition .

Contains the fire-retardant composition provided according to the invention in its most general formulation

a) a halogen-substituted aromatic hydroxy compound and

b) a compound containing phosphorus and / or antimony.

If the fire retardant compositions are intended to be added to laminates, it is important that the fire-retardant properties of the individual components a) and b) due to the properties used in the manufacture of the laminates Heat treatment are not destroyed. Obviously, this must be taken into account when choosing the individual components will. In the case of a laminate with a phenol aldehyde resin this heat treatment is usually carried out at temperatures of about 15o to 17o ° C .; the components a) and b) must therefore be chosen in such a way that they

109886/0486

Retardant properties are retained even if left at this temperature for at least an hour Area to be heated. Further, it is preferred that both the aromatic hydroxy compound and the Compound containing phosphorus or antimony in solvents such as alcohol, e.g. methanol, t \ uo1 or xylene, especially in alcohols, are soluble.

The preferred class of halogen-substituted aromatic hydroxy compounds a) are bromo-substituted Phenols, because these compounds containing bromine are more effective than corresponding compounds containing chlorine only halogen included. Usually the phenols with a higher bromine content are more effective fire retardant additives than those with a lower bromine content. For this reason the preferred ones are bromo-substituted Phenols such compounds as tribromophenol (formula 1 below) and a tetrabromobisphenol A (formula 2 below) t

Br

ib.

Jbr

1098 $$ / - 0Α8β

Examples of other suitable bromo-substituted phenols, which can be used for the fire retardant composition according to the invention are ortho-bromophenol, para-bromophenol or mixtures of both, a dibroraphenol, mixtures of a bromophenol and a dibromophenol, pentalbromo-p-phenyl-phenol and bromocresol. Although chlorine-substituted phenols generally have poorer fire retardant properties than have the corresponding bromine compounds, they are still effective; Examples of suitable chlorine-substituted ones Phenols are orthochlorophenol, parachlorophenol or mixtures of both, a dichlorophenol, mixtures of a chlorophenol and one of dichlorophenols, pentachloro-p-phenyl-phenol and chlorocresol. In the case of the phosphorus or antimony-containing compound b) of the fire-retardant composition, the Antimony compound, preferably antimony trioxide. Usually the phosphorus compounds are with a higher phosphorus content more effective fire retardant additives than those with a small phosphorus content. Examples of suitable phosphates are triisooctyl phosphate, trisethylhexyl phosphate, triphenyl phosphate, Tricresyl phosphate and trixylenyl phosphate. Aromatic phosphates, which generally have a lower polarity and having better plasticizing properties are generally preferred to aliphatic phosphates, especially if the composition in the manufacture of

109886/0486

Laminates used for electrical applications should be. The preferred phosphorus compound is trioxylenyl phosphate.

The preferred fire retardant composition according to the invention consists of a mixture of tetrabromobisphenol A. and trixylenyl phosphate. For the use according to the invention suitable bromine- and chlorine-substituted phenols as well as the phosphates can easily be prepared by standard processes many of them are commercially available.

In the fire retardant compositions according to the invention, the combination of a halogen containing aromatic results Hydroxy compound, preferably a bromine-substituted phenol, and those containing phosphorus or antimony Compound, preferably an aromatic phosphate such as trixylenyl phosphate, or antimony trioxide, a fire retardant Composition which, when used in laminate manufacture, gives results considerably better than those that would be expected based on the results obtained using either compound a) or b) alone or a compound containing both bromine and phosphorus or antimony in the same molecule would expect. With regard to the fire-retardant properties and the non-flammability results in the combination according to the invention, for example tetrabrombo-

- 7 -109886/0486

phenol A and trixylenyl phosphate, a synergistic one Effect, so that these properties are considerably better than those obtained with a corresponding amount of one of the two components alone achieved.

The best results are obtained when ingredients a) and b) of the fire retardant composition are in such Amount present that the ratio of bromine to phosphorus in the range between 2: 1 and 3o: 1, preferably in the range is between 4: 1 and 15: 1. Accordingly, the weight fraction of the compounds in the composition becomes so elected that this relationship is maintained; Depending on the ingredients actually used, the weight ratio can be between 40 and 150 parts by weight of the halogen containing aromatic hydroxy compound and between 15o and 40 parts by weight of the phosphorus or antimony containing Connection lie. When the composition is a mixture of tetrabromobisphenol A and trixylenyl phosphate exists, it is advantageous if the two constituents are present in approximately equal amounts by weight.

Synthetic resin paint

The fire retardant compositions of the invention can be used on a variety of materials

109886/0486

17718

and to give objects fire-retardant properties and ifichcsntflamrnt> arkelt. As mentioned above, are especially useful for creating fire retardant and Nichtentflammbarkeits properties in laminates .However, the inventive fire retardant compositions. For this purpose, they are expediently inserted into the laminate in such a way that they are added to the paint. The invention therefore also comprises a paint composition consisting of a thermosetting synthetic resin, a solvent for the synthetic resin and a proportion of the fire-retardant composition according to the invention which is between about 5 and about 80% by weight, preferably between about 25 and about 45% by weight on the weight of the pesticides in the resin. Preferably the thermosetting resin is a phenol aldehyde type resin. If it is desired for certain purposes, the coating composition can also contain customary additives, such as stabilizers, plasticizers or fillers.

These compositions are particularly advantageous when the fire retardant composition is also in the solvent for the synthetic resin is soluble, since then the paint composition is easier to apply and a greater shelf life Has. The most commonly used solvents for a phenol aldehyde resin are an alcohol, e.g. methanol, or

109886/0486
BATH ORIGINAL

a mixture of an alcohol with toluene; Antimony trioxide is in methanol or another synthetic resin solution not soluble and therefore, if used, must be dispersed or violently in the filler for the laminate Mix to be dispersed in the resin. For this reason, it is extremely preferred that the component b) the fire retardant Composition is a phosphorus-containing compound.

Laminates

In the production of laminates, which represents a further aspect of the present invention, a PUIlstoff is used treated with a thermosetting synthetic resin and a fire retardant composition according to the invention. Appropriately a paint composition, in which the Feuex'hemmindende composition is present, on webs of the Filler applied, the webs previously coated with a water-soluble, low-molecular synthetic resin of the same type, can be impregnated. The dried webs or plates are then dried, in part to evaporate the solvents and partly to harden the resin. A number of such plates are placed one on top of the other in a press or mold arranged and the stack is then subjected to the action of heat and pressure.

- Io -

109886/0486

BAD ORJGiNAL

While it is preferred for the simplicity of the process to thereby incorporate the fire retardant compositions into the To bring in laminates so that they can be added to the varnish, they can also be attached in other ways. So you can already at the stage of synthetic resin production by adding them to the reagents used to make the particular resin. Further they can also be added in a separate operation by simply adding the filler, before or after impregnation treated with the synthetic resin, with a solution of the fire retardant composition in a suitable solvent or by providing the fiber material with a coating of the fire retardant composition.

Accordingly, the invention also relates to a laminate consisting of one impregnated with a thermosetting synthetic resin A filler, the laminate containing a fire retardant composition according to the present invention. The filler is preferably a continuous fiber material such as paper and the synthetic resin is preferably a phenol aldehyde type resin. If the laminate is intended for electrical uses, it usually has a surface layer made of a metal, for example a copper foil.

- 11 -

109886/0486

The fire retardant compositions of the invention and optionally the lacquer compositions containing them are particularly useful in the manufacture of laminates, which are intended for electrical applications, because they offer an ideal balance of fire retardant and electrical properties, especially in terms of the dielectric constant and the power factor. In this context, the preferred composition of laok is one that contains, as synthetic resin, a cresol-formaldehyde resin modified with tung oil, which is obtained, by combining cresol, aqueous formaldehyde in molecular excess, and tung oil in the presence of an alkali all in one Allow solvents such as methanol to react with one another. As a fire retardant composition should be the varnish contain a mixture of a bromophenol and an aromatic phosphate. These compositions can be used be used to make insulating paper (electrical grade paper) for impregnation and to form laminates from it, which provide a well-balanced Relationship of fire retardant properties, electrical properties and punchability at room temperature exhibit.

The invention is illustrated below with the aid of a few examples described in more detail. In these examples, all specified amounts - unless otherwise specified - are parts by weight,

- 12 -

109886/0486

and the following synthetic resins or paints containing them are used:

Resin:

The synthetic resin used in each of the examples was a tung oil modified cresol-formaldehyde resin which was made by heating a cresol with aqueous formaldehyde in the presence of tung oil and ammonia as Catalyst.

Paint:

Except in cases where the fire retardant composition contains an antimony compound (antimony trioxide), In all other cases, the varnish was made by dissolving the desired amount of the respective fire retardant Composition in a - unless otherwise stated -47 #igen solution of the resin in methanol or a methanol-toluene mixture. The antimony trioxide containing fire retardant compositions are in the resin solution by vigorous stirring dispersed. The concentration of fire retardant compositions in each of the examples is up based on the solids content of the synthetic resin paint.

The fire retardant compositions in the individual examples are designated as follows:

109886/0486

A) Equal parts of tetrabromobisphenol A and trixylenyl phosphate with a bromine content of 4.7Ji and a phosphorus content of 0.06 # (Br: P = 7 · 8: 1).

B) Five parts of tetrabromobisphenol A and 5 parts of trixylenyl phosphate with a bromine content of 2.4 # and a phosphorus content of 0.3 # (Br: P = 8: 1).

C) 7 * 5 parts of tetrabromobisphenol A and 5 parts of trixylenyl phosphate with a bromine content of 3.4 # and a phosphorus content of o, j># (Br: P = 11: 1).

D) Io parts of tetrabromobisphenol A and 5 parts of trixylenyl phosphate with a bromine content of 3 »8 # and a phosphorus content of 0.3 # (Br: P = 12 · 5ϊ1) ·

E) 17 parts of tetrabromobisphenol A and 11 parts of trixylenyl phosphate with a bromine content of 7, oji and a phosphorus content of 0.6 # (Br: P = 11.5: 1).

P) tetrabromobisphenol A (for comparison).

G) trixylenyl phosphate (for comparison).

H) tris-dibromopropyl phosphate (for comparison)

-H-

109886/0486

I) 10 parts of tribromophenol and 12.5 parts of trixylenyl phosphate with a bromine content of 4.8 # and a phosphorus content of (Br: P = 7, otl).

? J) 7.9 TeileBromkresol and lo, 2 parts trixylenyl with a Bromgehali ^0, t%, and a phosphorus content of ο, ϋ # (Br: P = 4.3: 1).

K) 17 parts of a mixture of ortho- and parabromophenol and 11 parts of trixylenyl phosphate with a bromine content of 5.5 # and a phosphorus content of 0.6 # (Br: P = 9 * lsi)

L) 17 parts of a mixture of ortho- and parabromophenol and 2.8 parts of trixylenyl phosphate with a bromine content of 5.9 # and a phosphorus content of 0.2 # (Br: P = 29: 1).

M) 7.9 parts of a mixture of 82 # parabromophenol and 18 # 2,4-dibromophenol and 1.2 parts of trixylenyl phosphate with a bromine content of 2.8 # and a phosphorus content of 0.6 g (Br: P = 4.7: 1).

N) 5 parts of pentachloro-p-phenylphenol and 5 parts of trixylenyl phosphate with a chlorine content of 2.3 # and a phosphorus content of 0.3 # (Cl: P = 7.8: 1).

10S886 / 0486

Q) 12.5 parts of tetrabromobsphenol A and 12.5 parts of antimony trioxide with a bromine content of 4.7Ji and an antimony content of 6.6 # (Br: Sb = 0.7: l)

Two types of laminates were used in the examples. They Were Made In The Following Ways:

Laminate X

Electrical grade kraft paper was preimpregnated to a resin content of 14 # with a low molecular weight, water soluble phenol malaldehyde resin obtained by reacting phenol with a molecular excess of an aqueous formaldehyde in the presence of alkali. This pre-impregnated paper was further impregnated with the respective phenolic resin varnish so that it had a total resin content of $ 53 after drying. The treated paper was cut into a suitable size, and seven layers thereof were stacked one on top of the other and then heated in a press between stainless steel plates for 50 minutes at 15 ° C and a pressure of 10 5 kg / cm. The product was chilled for J> o minutes.

Laminate Y

This is a copper-clad laminate made using the same process as laminate X.

- 16 -109886/0486

with the exception that a copper foil (about 3o5 gr / m), which was coated with a mixture of iron phenolic resin and polyvinyl butyral as an adhesive, on one surface of the seven-ply stack was arranged.

The various tests carried out in the examples in connection with the properties of the laminates were, with the exception of the tests mentioned in Examples 2 and 3, according to the following standard procedures urü standards carried out.

Insulation resistance BS 2782, 2o4 A Power factor BS 2782, 2o7 B Electrical strength BS 2572, App P Water absorption BS 2076, App E

Punching properties (room temperature)

Resistance to solvents

Fire retardancy

ASTM test D-617-44

5 minutes exposure to trichlorethylene vapor

determined by measuring the self-extinguishing time according to BS 3888, 1965, App T.

(BS = British standard)

example 1

X laminate was made using a varnish, the loo parts of the resin and 25 parts of the fire retardant composition A, that 25 wt.%, Contained.

- 17 109886/0486

When tested for fire-retardant properties, this laminate showed a self-extinguishing time of less than 15 seconds as opposed to 90 seconds or more for a comparable one Product without fire retardant additives.

Example 2

Laminate Y was made using the same varnish as in Example 1. Some of those of interest here Properties of this copper-coated laminate and the paper carrier material after etching away of copper are given in Table 1 below.

Example 3

Laminate Y was made using a varnish, 100 parts of the resin and 25 parts of the fire retardant Composition Q contained. Some of its properties are also in Table 1 below specified.

- 18 -

1 09886/0486

TABEL

Properties of the
Laminate units Test results
Ex. 2 Ex. 3 layers
The bubble image
2hen the shift Test method LI l-lo .11 j 16 Solder flow
unetched samples
etched samples no BIa
separation
between
th 8th NEMA LI l-lo .12 18th Peel strength
after solder flow lbf / in 8th 8th NEMA
1965
NEMA
1965 LIl- Io .13 after heating 8th 3 x 10 ° ASTM D 257 Specific resistance
after 96 hours at
35 C and 90 # RH
f Megohm cm 6 χ ίο ⁶ k
2 x ItV ASTM D 257 ]
JQ surface resistance
INACH 9o St. at 35 ⁰ C
! and 90 # RH Megaohm 7o, ooo Properties of the
Paper carrier after
Etching away the copper o.o4o ASTM D I50 Power factor at
lo ^b Hz after 48 hours
in water at 50 ° C Tg £ o.o4o 4.8 ASTM D I50 Dielectric con
constant at 10 ° Hz nacl
18 hours in the water at
50 ° C 4.2 > 5o NEMA
1965 LI l-lo. Electric power supply
(parallel to Schich
th after 48 hours in
Water at 50 C) KV > 5o I8, loo
16,300
o, 53 NEMA
1965
ASTM LI l-lo.
D 229 t Flexural strength
Longitudinal direction
Transverse direction
I.
I.
!
iWater absorption after
; 24 hours at 23 ° C lbf / in ²
lbf / in ²
% I9,6oo
17,000
o, 57 5 ASTM D 229 Self-extinguishing time
I. sec. 6th

109886/0486 - 19 -

The fire retardant used in Examples 1 to 3 Compositions did not result in any noticeable Impairment of the important electrical and other properties of the laminates formed and they showed also no premature dislocation during the heat treatment of the laminates. The in Examples 1 and 2 The fire retardant composition A used had the advantage that it is soluble in the resin solvent so that the Handling problems are reduced. The shelf life of the paint composition was not impaired. The combination of good electrical properties, cold stamping properties and self-extinguishing properties make the Laminates according to Examples 2 and 2 are particularly suitable for the production of printed circuits and for others electrical applications.

EXAMPLE 4

This example shows how a change in the amount of the two constituents of the particular fire retardant composition as well as the concentration of the composition affect in a particular synthetic resin.

Tell a:

Laminate Y was made using a lacquer composition containing 100 parts of the resin and 25 parts of the

- 2o -109886/0486

fire retardant composition A, i.e. 25 wt. #.

Part B:

Y laminate was prepared using a resist composition loo parts of the synthetic resin and Io parts of the fire retardant composition B, ie 17> 6 wt.% Contained.

Part c:

Laminate Y was made using a varnish composition containing 100 parts of the synthetic resin and 12.5 Parts of Fire Retardant Composition C, i.e. 21 wt. #, Contained.

Part German

Laminate Y was made using a varnish composition containing 100 parts of the resin and 15 parts of fire retardant composition D, i.e. 24 parts by weight, contained.

Part e:

Laminate Y was made using a varnish composition which contained 100 parts of the synthetic resin and 28 parts of the fire-retardant composition E, i.e. 4.5% by weight.

- 21 -

109886 / 0A86

Various properties of the protective fabrics were determined and the results are given in Table II below:

TABLE II

characteristic unit a part
bc 4oö, ooo
o, ol8 d e [solation
miderstand
Power factor
at 800 \\ 2 Megohm
tg £ 128, ooo 4oo, ooo
0.019 **> 4oo, ooo
o, ol9 30,000
0.031 Electric
strength KV / inch 426 44o 11 42o 270 Water absorption mg 13th 11 80 12th 2o Display
societies
(Room tap _% 9o 80 2o 65 90 Self-extinguishing time sec. 6th 2o 18th 6th

The results show that the most favorable balance of fire retardant electrical water absorption and punching properties was obtained with a laminate containing the fire retardant composition A.

Example 5

This example is included for comparison purposes and shows the superior results obtained using a typical fire retardant composition according to the invention

109886/0486

- 22 -

gets compared to the results one gets when using
of the individual components of the composition or under
Using a compound that contains bromine and phosphorus in the same molecule is achieved.

Tell a:

Laminate Y was made using a lacquer composition containing 100 parts of the synthetic resin and 12.5 parts of the fire retardant F, ie tetrabromobisphenol A alone
contained (Br content = 4.7 #).

Part B;

Laminate Y was made using a paint composition containing 100 parts of the resin and 25 parts of the resin
fire retardant Q, ie trixylenyl phosphate alone
contained (P content = 1.2 #).

Part c:

Laminate Y was made using a paint composition containing 100 parts of the resin and 25 parts of the resin
fire-retardant agent H, ie containing tris-dibromopropyphosphate alone (Br content = t% and P content = o

Part d:

Laminate Y was made according to the procedure described in Example 4, part a, i.e. it contained 12.5 parts of the

- 23 109886/0486

fire retardant P and 12.5 parts of fire retardant O (fire retardant composition A).

Various properties of the laminates were noted, the results are shown in Table III below reproduced:

Table III

characteristic unit t
a part
b c - ■ - d Isolation
«Riderstand Megohm 467, ooo Io3, ooo - it;
learning 128, ooo Power factor tg £ o, o33 o, o55 - 0.032 Dielectric
constant
Water absorption KV / inch
mg 3.96
0.8 4.13
16 3.90
13th Bt display
Shafts * 75 7o 90 Solvent-
resistance Well; germ
Marble
tion Schlec
strength
marble Well; no
Marbling 3 self-extinguishing time sec. 18th 15th 6th

109886/0486

These results show that a laminate that .als fire retardant containing only the bromine compound, relatively poor fire retardant properties and cold stamping properties and that the laminate containing only the phosphorus compound was relatively poor Properties in every respect, but especially with regard to the electrical properties, the water absorption and solvent resistance. The fire retardant H (part c) decomposed prematurely during the hardening of the laminate, which charred so that it was completely unusable for practical use. Again, the most balanced ratio of properties results from the laminate, which is fire-retardant Composition A contained (part d).

Be ispiel 6

Y laminate was prepared using a resist composition loo parts of the resin and 22.5 parts of composition I feuerheramenden, ie 15 wt.%, Contained.

Laminate properties;

Power factor o, o42

Dielectric constant 3> 8o

Water absorption 12

Punching properties 90

Self-extinguishing time Io sec.

- 25 109886/0486

Example 7

Laminate Y was made with a Laok composition, the loo parts of the synthetic resin (42-lge solution in Methanol) and 18.1 parts of fire retardant composition J, i.e. 12.8 parts by weight.

Laminate properties:

Power factor 0.036

Water absorption 8

Die cutting properties 85

Self-extinguishing time I3 sec.

Example 8

Y laminate was prepared with a coating composition, the loo parts of the resin (37 # solution in methanol) and 28 parts of the fire retardant composition K, ie 43 wt -.%, Contained.

Laminate properties;

Power factor 0.036

Water absorption 6

Punching properties 90

Self-extinguishing time 14 sec.

Example 9

Laminate Y was made with a lacquer composition containing 100 parts of the resin (40 # solution in methanol)

- 26 109886/0486

and 19.8 parts of fire retardant composition L, i. 33 Oew .- #, contained.

Laminate properties:

Power factor o, o24

Water absorption 7

Punching properties 9o

Self-extinguishing time 17 sec.

Example Io

Laminate Y was made with a paint composition containing 100 parts of the resin and 18.1 parts of the fire retardant composition M, i.e., 30 wt. Ji.

Laminate properties;

Performance factor water absorption Punching properties

Self-extinguishing time

Example 11

Y laminate was prepared with a coating composition, the loo parts of the synthetic resin and the fire retardant composition components Io N, ie, 8 wt -.% "Contained.

Laminate properties :

Power factor o, o2o

Water absorption 12

Punching properties 8o

Self-extinguishing? t 2o sec.

- 27 10988 6/0486

O, o33 8th 8o 11 Sec.

Claims (1)

Claims 1. Fire retardant composition characterized in that it is a) a halogen-substituted aromatic Hydroxy compound and b) a compound containing phosphorus and / or antimony. 2. Composition according to claim 1, characterized in that g e mark Chnet that the compound a) a chlorine- or bromine-substituted phenol and the compound b) a aliphatic or aromatic phosphorus-containing compound or antimony trioxide. 5. Composition according to claim 1 or 2, characterized in that the compound a) is a bromine-substituted Phenol and the compound b) is an aromatic phosphorus-containing compound or antimony trioxide. 4. Composition according to claim J5, characterized in that the aromatic phosphorus-containing Compound is an aromatic Pho.sphat. - 28 - 109886/0486 5. Composition according to one of Claims 1 to 4, characterized in that the two compounds a) and b) are chosen so that they retain their fire-retardant properties after heating to a temperature of 15o to I ^{1 ° C for about one hour.} 6. Composition according to any one of claims 1 to 5 * characterized in that the compound a) orthobromophenol, parabromophenol, a mixture of both, a dibromophenol, a mixture of a bromophenol and a dibromophenol, pentabromo-p-phenylphenol or bromocresol is. 7. Composition according to any one of claims 1 to 5> characterized in that the compound a) is tribromophenol. 8. Composition according to any one of claims 1 to 5 j characterized in that the compound a) is tetrabromobisphenol A. 9. Composition according to one of Claims 1 to 8, characterized in that the compound b) Is trixylenyl phosphate. - 29 - 109886/0486 10. Composition according to one of claims 1 to 9 * characterized in that the compound a) is a bromine-containing compound and the compound b) is a Phosphorus-containing compound is, and that the compounds are present in such amounts by weight that the ratio of bromine to phosphorus is in the range from 2: 1 to 10: 1. 11. The composition according to claim lo, characterized in that the ratio of bromine to Phosphorus ranges from 4: 1 to 15: 1. 12. The composition of claim 1, characterized in that τ indicates that it contains approximately equal parts by weight of tetrabromobisphenol A and trixylenyl phosphate. 13 · A fire retardant composition according to any of the Materials or articles containing claims 1 to 12. 14, synthetic resin paint composition comprising a thermosetting resin and a solvent for the Kunstkarz, characterized in that the composition further comprises between about 5 and about 8o wt -.%, Based on the Peststoffgehalt of the resin, a fire retardant composition according to any one of claims 1 to 12 contains. 109886/0486 15 · The composition of claim 14, characterized in that it is between about 25 and about 45 wt -% contains the fire retardant composition.. 16. Thermosetting synthetic resin laminate, consisting of a filler impregnated with a thermosetting synthetic resin, characterized in that the oiler comprises a fire retardant composition according to any one of the claims 1 to 12 contains. 17. Laminate according to claim lö, characterized in that the filler material with a synthetic resin lacquer composition impregnated according to one of claims 14 or 15 is. 18. Laminate according to claim lö or YJ, characterized in that it has a metal coating. 19. Laminate according to claim 18, characterized in that that the metal plating is a copper foil. 1Q9886 / 0486