CA2042840C

CA2042840C - Preparation and use of resins that are relatively non-inflammable and resistant to high temperatures

Info

Publication number: CA2042840C
Application number: CA002042840A
Authority: CA
Inventors: Herbert Schreiber; Gunter Burkart; Bruno Knaus
Original assignee: Gurit Essex AG
Current assignee: Huntsman Advanced Materials Switzerland GmbH
Priority date: 1990-05-21
Filing date: 1991-05-17
Publication date: 1996-11-26
Anticipated expiration: 2011-05-17
Also published as: JP3203385B2; CS145891A2; EP0458739A2; EP0458739A3; CA2042840A1; JPH04227922A; DE4016296C1; KR0166377B1; AU636226B2; AU7721391A; KR910020104A; ZA913434B

Abstract

Polymeric resins which are difficultly inflammable and/or resistant to high temperatures are obtained by curing a curable resin mixture which comprises a mixture of:
(a) a component consisting of at least one thermically curable 1-oxa-3-aza tetraline groups containing compound;
(b) a component consisting of at least one curable halogenated epoxy resin; and optionally (c) a component consisting of at least one curable non-halogenated epoxy resin; and/or optionally (d) a curing agent for epoxy resins.
By tempering them, the glass transition temperature and the mechanical properties can be further improved.
The obtained polymeric resins may be used as follows: as electric insulating materials, in particular for printed circuit boards; in aircraft constructions, also for supporting structures; adhesives; and moreover wherever resins which are flame-resistant are to be used.

Description

1- 204~8~0 PREPAP~ATION AND USE OF RESINS THAT ARE RELATIVELY NON-INFT~ rMAFiT~ AND RESISTANT TO HIGH TEMPERATURES

FIELD OF THE INVENTION
This invention refers to resin mixtures which may be cured to form polymeric resins which are difficultly inflammable and resistant to high temperatures; to a method for preparing said polymeric resins; as well as to the use of said polymeric resins.
BACKGROUND OF THE INVENTION
Compounds containing 1-oxa-3-aza tetraline groups and their prepolymers (hereafter jointly called "oxazene resins" by convenience) are known, for example from the publications CH-A5-574,978, CH-A5-579,113 and CH-A5-606,169.
From the publication EP-A1-0,356,379 a resin mixture is known which may be cured to form polymeric resins which are difficultly inflA~l-~,hle and resistant to high temperatures. Said resin mixture i5 at least partially a mixture of:
(a) a resin component comprising or consisting of at least one thermically curable 1-oxa-3-aza tetraline groups

2 0 containing compound; and of (b) a flame retardant which is not miscible with resin component ( a );
and optionally also contains at least one curable epoxy compound.
It is true that by curing said known resin mixture, products which are difficultly inflammable and resistant to high temperatures may be obtained. However, their properties are still not suf f icient for many uses, since the mechanical and ' electrical properties are deteriorated by the flame retardant additive ( b ) .
SUM~ARY OF THE INVENTION
An object of the present invention is to eliminate the disadvantages of the prior art described above, and to further improve the behaviour in f ire of oxazene resins without deteriorating their other properties.
According to the present invention, this object is met by a resin mixture which may be cured to form a polymeric resin 10 which is difficultly inflammable and/or resistant to high temperatures, said resin mixture comprising (a) a component consisting of at least one thermically curable 1-oxa-3-aza tetraline groups containing compound;
(b) a component consisting of at least one curable halogenated epoxy resin; optionally (c) a component consisting of at least one curable non-halogenated epoxy resin; and/or optionally (d~ a curing agent for epoxy resin~

`~ 2042~9~

The compounds containing 1-oxa-3-aza tetraline grouPs of component (a) are obtained, for example, from Phenols bY re~c-tion with formaldehYde and an amine, approximately according to formula (A):
1~ ~ 2 11 $,~ ( A ) R , ~ ~ , 1-oxa-3-~za tetral ine group Por example, R is hydrogen, halogen, alkyl or alkoxy, and R ' i g a n a 1 i Pha t i c or aroma t i c group .
However, the comPounds cont~ i n i ns 1-oxzl-3-~ za tetra 1 i ne groups of comPonent (a) can also be PrePared by other methods resulting into simi lar products .
In contrast to other known condensation reactions of Phe-nols, ~mines and formaldehYde, in the reaction outlined above phenolic OH-grouPs are consumed. It is thereby Possible, ac-cording to the formula (A) hereinabove, to determine the amount of the synthesized 1-oxa-3-aza tetraline groups from the ana-lytic determination of the said OH-grouPs in the reaction mix-ture .
PrePolymers of 1-oxa-3-aza tetraline groups containing com-pounds are Z!180 useful for PreParins said oxazene resins. ~ince ~ome of the 1-oxa-3--aza tetraline grouPs may react during poly-20~2840 said 1-oxa-3-aza tetral ine groups than provided by the monomers used to form such Prepolymers. However, it is essential that the intermediately formed or hypothetic monomer reaction pro-duct does in fact contain 1-oxa-3-aza tetral ine groups . This can easily be calculated by a Person skilled in the art from the functional itY, An 1-oxa-3-aza tetral ine comPound, or its PrePolymer, useful in accordance with the present invention is, for example, formed if the molar ratio is kept within the lim-its defined in the abovementioned Publication CH-AS-606,169.
Phenol or phenol derivatives as well as amines and formal-dehyde are used as starting or basic materials for preParing the oxazene resin.
Preferably, for the present invention, 1-oxa-3--aza tetra-l ine groups containing comPounds are used which are formal ly derived from a Phenol and an amine, one of said components be-i ng more than mo no f un c t i o n a l .
Examples of Phenols which can be used are:
-- Monovalent Phenols, such as phenol, m- ~nd P-cresol, m- ~Ind p-ethyl Phenol, m- and p~isoPropyl phenol, m- and P-isoPro-PYIoxy Phenol, m-- and P-chloro Phenol, and beta-naphthol.
Para- and met~-sub3tituted phenols are Preferred, since they do not include anY blocked reactive positions. Also preferred are the Phenols which are not alkYl substltuted and not alkyloxY substituted, resPectivelY.
- Bivalent Phenols, such as 4,4 '--dihydroxydiphenyl methane,

3, 3 ' -dihYdroxydi Phenyl methane, 2, 2 ' -bis- (4-hYdroxYPhenyl ) propane, 4,4'-dihydroxy stilbene, hYdroquinone, and resor--cin .

2-~428~0 . .
.

- Low-condensed Phenolic formaldehYde novolak resins, eventu--al ly mixed with a phenol .
Examples of amines which are particularly useful are:
-- Aniline, phenylene diamine, benzidine, diaminodiphenyl methane, 2,2'-bis-(aminoPhenYl~ propane, cYclohe~ylamine, ethylenediamine and proPYlenediamine, in particular P-phenYlenediamine and 4,4'-diaminodiPhenyl methane, aromat i c ami nes be i ng pre f erred .
Also particularly useful are 1-oxa-3-aza tetraline com-pounds which are derived from a novolak and an aromatic amine, PreferablY from a novolak having a degree of polYmeriz~tion of about 2 and of aniline, or from phenol and an aromatic diamine.
Preferably, the second component (b) comprises or consists of:
-- one or several glYcidyl ethers of halogenated Phenols, in Particular POlyvalent phenols, -- one or several glYcidyl ethers of condensation Products of h~logenated Phenols with aldehYdes or ketones, or -- one or several glYcidyl ethers of halosenated novolak3.
ParticularlY useful are the glYcidyl ethers of halogenated bisPhenol A or of halogenated bisphenol ~, in particular tetra-bromo bisPhenol ~ or tetrabromo bisPhenol F, as wel 1 as bromin-a t e d novo 1 aks .
Prefer~bly, the halogenated epoxY resin of component (b) is a brominated epoxY resin.
Such brominated ePoXy resin3 are known and commercial ly avai lable. Also, they were already proposed, a3 sole component, for Preparing difficultlY inflamm~ble PolYmeric resins. How-ever, ~aid polYmeric resins show the fol lowing essential draw-1~ . .~ 1, ~ .

204284a - They have gla~s transition temperatures which are too low.
- In the case of combustion, they produce con~ider~ble qu2n-tities of the highlY toxic carbonyldibromide, due to their high bromine content.
-- They are expensive.
Product No .
(Trade Name: "D.E.R. 511-A 80" of The Dow Chemical CompanY):
Brominated epoxY re~in of the bisphenol-A type in an ace-tone solution.
Epoxide equivalent weight 1) 445... 520 Visc03ity (25C): 1000.. 4000 mPa-s Non-volati les: 80+1 percent bY weight Solvent: Acetone Color ~ccording to Gardner, m~ximum: 5 Bromine content 1): 19.... 21 percent bY weight Flash point (T.O.C. ): 63 C
Product No. 2 (Trade Name: "D.E.R. 511-EK 80" of The Dow Chemical Company):
Brominated ePOXY resin of the bisphenol-A tYPe in a methyl ethyl ketone ~olution.
Epoxide equivalent weisht 1): 445... 522 Vi~cosity ~25C): 1000.. 4000 mPa c~
Non-volatiles: 80+1 percent bY weiyht Solvent: MethYl ethyl ketone Color according to Gardner, m~x i mum: 9 ~ _ Bromine content 1) 19.... 21 percent by weight Fla~h point (T.O.C.): 52 C
* a trade-mark ~ -- 7 20428~0 Product No. 3 (Trade Name: "D.E.R. 512-A 80" of The Dow Chemical Company):
Brominated epoxY resin of the bisPhenol-A type in an ace- -tone solution.
Epoxide equivalent weight 1) 480... 560 Viscosity (25C): 700... 2500 mPa-Non-volatile3: 80+1 percent bY weight Solvent: Acetone Color according to Gardner, maximum: 5 Bromine content 1 ~: 21 . . . 22 , 5 percent bY weight Flash point (T.O. C. ): 56 C
Product No. 4 (Trade Name: "D.E.R. 512-EK 75" of The Dow Chemical ComPany):
Brominated epoXY re:3in of the bisPhenol-A tYpe in a methyl ethYl ketone solution.
Epoxide equivalent weight 1) 480... 560 Vi~co-~itY (25C): 500... 1500 mPa s Non-volatiles: 75+1 percent bY weight Solvent: MethYl ethYl ketone Co l or ~ccord i ng to Gardner, maximum: 3 Bromine content 1) 21.... 22,5 PerCent bY weight Flash point (T.O.C.): <-2 C
Product No. 5 (Trade Name: "D.E.R. 512-EK 8~' of The Dow Chemical ComPany):
Brominated epoxy resin of the bi~Phenol-A tYPe in ~ methyl ethYl ketone solution.
Epoxide equivalent weight 1) 480... 560 Viscosity (25C): 1000.. 3500 mPa-s Non-volatiles: 80+1 Percent bY weight Solvent: MethYl ethyl ketone * a trade-mark _ .~
... ~
. ~

20~2840 Color according to Gardner, maximum: 5 3romine content 1) 21.... 22,5 percent by weight Flash point (TØC. ): 52 C
Product No. 6 (Trade Name: "D.E.R. 521-A 80" of The Dow Chemical Company):
Bromin~ted ePOxY re~in of the bisPhenol-A tyPe in an ace-tone solution.
Epoxide e~uivalent weight 1) 430,.. 475 Viscosity (25C): 1000.. 4500 mPa-s Non-volatiles: 80+1 percent by weight Solvent: Acetone Color according to Gardner, maximum: 6 8romine content 1) 19.... 22 percent by weight Flash point (T.O.C. ): 63 C
Product No. 7 (Trade Name: "D.E.R. 542" of The Dow Chemical ComPanY):
~rominated ePOXY resin of the bisPhenol-A tyPe.
Epoxide equivalent weight 1) 305,.,355 Softening point according to Durran: 50,5.. 62,5 C
8romine content: 44.... 49 percent by weight Flash point (T.O.C. ): 199 C
Product No. 8 (Trade Name: "D.E.R. 566-A 80" of The Dow Chemical ComP~nY):
~3rominated epoxy resin of the bisPhenol-A tyPe in an ace-tone solution.
EPoxide e~uivalent weight 1) 410... 450 Viscosity (25C): 800... 4000 mPc s Non-volatile: 80+1 percent by weight * a trade-mark ~; ~
.. , .. _ , ... . . . _ Solvent: Acetone Color accordins to Gardner, maximum: 5 Bromine content 1) 18.. 20 percent bY weight Fl ash poi nt (T . O . C . ): < 2 C
Product No. 9 (Trade Name: "QUATREX 6410'' of The Dow Chemical ComPany):
Brominated epoxY resin of the bi~phenol-A type.
Epoxide equivalent weight 1) ~50 Softening Point: 80 C
Viscosity (150C): 0,0180 m2.3-1 Hydrolyzable chloride: <150 ppm Volatiles: <0,25 percent bY weight Bromine content: 47.. 51 percent bY weight Glass transition temperature ~fter phenolic curing: 175 C
1) Based on the solids content PreferablY, the halogen content i~ le3s th~n 3 gram equiva-lents, in Particular less than 2 equivalent3, based on 1 kilogr~m ot the total weight of the abovementioned components (a) to ~d).
Consequently, in resins containing a brominated expoxy re~in as comPonent (b), the bromine content is PreferablY lesq than 24 percent bY weight, in Particular le~s than 16 percent by weight, based on the total weight of the resin. Even with bromine con-tents as low as 7.5, 2.5, and 1 Percent by weight, respectively, flame retsistant can be obtained.
* a trade-mark 2~4284~

Preferably, the quantitY of component (b) is le58 than 50 percent by weight, in particular less than 30 Percent by weight, based on the total weight of the resin (component (a) + com-ponent (b) ) . However, fl~me re3istant resins are already ob-tained with quantities of less than 15 Percent bY weight, or of less than 5 percent by weight, or even of less than 2 Percent by weight of component (b), based on the total weight of the resin.
The fact th~t the advantages described hereafter may be ob--tained with such sm~l l quantities of the component (b), in par-ticular of a brominated epoxy resin, was highlY surprising to a person ski l led in the art.
It iB a particular advantage that - beside an essential lY
improved thermic behavior in combination with excellent electri-cal properties which will be explained hereafter in detail - in the c~se of combustion theY Produce onlY smal l quantitie-q of toxic comPounds, and that only a small quantity of the expensive component (b) must be used.
The mixture according to the invention may also comprise a component tc) comPriSing or consisting of at least one non-halo-genated ePOxY resin. AdvantageouslY, the quantitY of said com-ponent (c) iq les3 th~n the qUantitY of comPonent tb), and Pre-ferably les3 than h~lf the quantitY of component tb).
Such suitable epoxy resins ~re in particular monofunctional or multifunctional epoxy compounds which can be cured thermical-ly, catalyticly or bY means of a curing ~gent.
The mixture according to the invention may also comprise as component td) ~ curing agent for ePOXY resins. Polyvalent amines, Polyvelent carboxylic acids and their anhYdrides, di-cyano diamide, as well a~ novol~ks are ParticularlY useful aq such curing agents.

2~42~4~

Suitable epoxy comPounds and curing agent ~re, for example, described in:
-- Sidney H. Goodman, Handbook of Thermoset Plastics, Noyes Publications, Park Ridge, NJ:
- W. G. Potter, EPoxide Resins, Ilife Books, London:
- Henry Lee ~nd Kris Nevi 1 le, Handbook of EpoxY Resins, McGraw-Hill Book ComPanY, New York/San Francisco~Toronto/
London .
By therm i c a l l Y c ur i n g the aboYeme nt i on e d c ura b l e re 9 i ns at a temperature of above 100 C, in particular at a temPer~tUre of 140 to 220 C, PolYmeric resins which are difficultly inflamma--ble, resistant to high temPer~tures and heat resistant can be obta i ned .
Surprisingly, the ProPerties of the Polymeric resins cured as explained above can sti l l be considerably imProved bY a ther-mic aftertreatment. Thus, for ex~mPle, ~Y temperlng them for 24 hours at a temPerature of 220 C, the glass tran3ition tempera-ture ri3es up to more thiln 280 C.
Advantaseously, the cured polymeric resins are subiect to said thermic aftertreatment at a temPerature of 180 to 250 C, and PreferablY at a temperature of 200 to 230 C. The duration of said temPering dePends on the temperature . The fol lowing standard values maY serve as a basis however, the durations can be extended at wi l l without deterioration of the PolYmeric res-ins:
Curing:

4 hours at 180 C: or 2 hours at 200 C.

`~ 20~28~0 Tempering:
24 hours at 220 C.
Also, these durations can be proportionally combined at will.
For example. the following temPering cycle has proved its value:
30 minutesJ200 C + 30 minutes/220 C + 30 minute~/230 C
30 minutes/250 C.
The ProPerties of the Polymeric resins Produced as described ~bove can be tailored for cert~in aPplicationq bY addition of usual additives . The fol lowing additives are of particular im-port~nce:
reinforcement fibers, such as glass, ~uartz, carbon, mineral and synthetic fibers, in the usual forms of short fibers, staPle fibers, thre~d3, fabrics or mats:
plastici2ers, especially phosphorous compound~:
c~rbon black or graPhite:
fillers;
dye~tuf fs:
micro hol low sPheres:
metal Powder:
catalysts and flame retardants, in particular the following groups of com-pounds, and comPounds, resPectivelY:
aluminium hydroxide:
hydrated calcium magnesium carbonate:
magnesium hydroxide:
e l ementa l red PhosPhorous:
oxygen acid~ of Phosphorous:
inorg~nic salts of oxygen acids of PhosPhorous:
org~nic 3alts of oxygen acids of phosphorous;
po lYphosph~tes .
boric acid:

4284~

The methods known for processing thermic~l ly cur~ble Phenol formaldehyde resins or EP resins, such as hot-pressins of pre-pregs, SMC (Sheet Molding ComPound): or molding of molding com-pounds, c~sting, filament winding, vacuum imPregnating, may be used for Proce3sins the resins according to the invention.
The PolYmeric resins which can be obtained by curing, or by curing followed by tempering the resins according to the inven-tion, ~nd which are difficultlY inflammable ~nd resistant to high temPer~tures, are particularly suitable for the following u~es:
- ~ electric insulating materi~ls, in P~rticular for printed circuit boards:
- for supporting structures, in Particular in aircr~ft con-struct i ons -- wherever resins which ~re flame-re~i tant or resistilnt to hish temPer~tures are to be used;
- as adhesives.
EXAMPLES
1. St~rting m~terial~ --The following starting materials are used in the following exam ~ l~s -~ 2042840 Component (a):
(A/1) Oxazene resin 1Reaction product of phenol with aniline and formaldehyde in ~ molar ratio of 1:1:2, having the structural formula:

( A/2 ) Oxaze ne res i n 2 Reaction Product of 1 mole (2 e~uivalents) of the novolak obtained bY reacting 2 moles of Phenol and 1 mole of form~ldehYde, with 2 moles of aniline and with 4 moles of formaldehyde, having the the following average composi-tion:
~~ N~c~l2~N ~
(A/3) Oxazene regin 3 Reaction Product of 4,4'--di~mino-diPhenYlmeth~ne with phenol and formaldehYde in a molar ratio of 1:2:4, having the ~ tru c tura l f ormu l a:

-~ 42~0 ~N~CHz~N~
Component (b):
(B/1) Brominated ePoxy resin 1 - -"D.E.R 542" of The Dow Chemical Company Bromine content, based on solids: 44..... 49 Percent by weight (BJ2) Brominated ePOxY resin 2 "Qu~trex 6410" of The Dow Chemical ComPanY
Bromine content, based on solids: 47...51 percent by weight Reinforcins material (R) Glass cloth "Type 90085" of Interglas--Textil GmbH
Surface densitY: 108 g/m2 Number of threads/cm: 24x24 EpoxY silane fini~h 2. Prep~ration of samples The components 3Pecified in Table 1 were mixed under re-duced Pressure at 100 bi~ 130 C. Then, the s~mPles for the thermal analysi~ were withdrawn. The remainder was soaked up, with or without glass cloth, between tef lonized glass Plates ~nd cured in an circulating air oven for 2 hours at 200 C.

.
2~42~40 The term "Ref . " means the intern~l reference number of Ap--P l i cant .
3. Flame-resistance test The flame-resistance test was made according to UL Specifi-c~tion 94 (Vertical Test), abreviated: "UL 94" (cf.: Jurgen Troitzsch. Brandverhalten von Kunststoffen (1982 Munich/Vienna ISBN 3-446-13391-7), Pages 396 to 399).
The results are compiled in Table 1.
It was surPrising that Class UL-94-V0 can alre~dy be ob-tained bY an addition of 20 percent bY weight of brominated epoxy resin, for glass cloth reinforced samples alre~dY by an addition of 10 percent bY weight.
4 . Me chan i ca l Prop ert i es The mechanical properties and the glass transition temPera-ture Tg (also called "glass temPer~ture") were determined, with or without tempering, by means of - DCS ("Differenti~l Sc~nning Calorimetry"), -- DMA ~"Differential Mechanical AnalYsi~"), and - TMA ("Thermo Mechanic~l AnalYsis").
The results are compiled in Table 2.
It was extremelY surPrising that the rise in the glass tranE~ition temperature obtainable bY a temperins is associated with an essentially reduced drop of the E' module at thi~3 tem-Perature ~cf. in Parti.n~ .. S~.m~lQ.~ f 1~ 71_r~

~ 428~0 Table 1: Composition of s~mples (P~rts by weight) Flame-resistance test according to UL 94 .

SamPle < - ComPosition---- > <-Fl~me resistance UL 94-> Ref.
No.<----(a~---> <-(b)-> Glass Thick- Duration of Class A/1 A/2 A/3 B/1 B~2 R ness combustion 1 ayers mm s 1st 2nd ignition 0, 80 4, 0 4, 8 V1 Kb70 2 90 10 9 0,92 2,8 3,0 V0 Kb70-G
3 80 20 0, 80 1, 7 0, 7 V0 Kb71 4 80 20 9 0, 90 1, 5 0, 5 V0 Kb71--G
1, 00 0, 0 2, 0 V0 17-1 6 85 15 1, 03 0, 0 0, 3 V0 17-3 7 80 20 1, 05 0, 0 0, 0 V0 17-2 8 90 10 1,07 11,7 14 V1 17-4 9 85 15 1, 03 6, 7 7, 3 V1 17-6 1, 04 1, 7 3, 7 V0 17-5 11 95 5 9 1, 04 10 3 V1 17-9 12 97,5 2.5 9 1,02 13 10 V1 17-8 13 99 1 9 1, 02 33 10 V1 E1 14 80 20 1, 00 3 2 V0 E2 Comparative test ---- 100 9 1, 02 Burns up to top 17-7 `~ 20~2840 Table 2: Mechanical propertie3 SamPle Curing/ <~ Strength-------> <----DMA- -> TMA DCS Pef.
No.temper- 3ending E module Thick- 1), 2) 3) 4) ing~trength ness E'go E' 180 Ts Ts h/CN/mm2 N/mm2 mm GPa GPa C C
2/200 4.8 1.2 182 171 K~70 22/200 522+14 23'500 0.91 2.7 2.4 Kb70-G
32/200 118+5 11,800 0.85 5.8 178 K~71 +24/220 103+21 14,800 5.7 4.9 +72/220 112+29 14,400 5.4 4.7 42/200 495+14 22,300 0.91 3.0 1 6 178 Kb71-G
+ 2/220 4, 4 4, o +24/220 8 . 5 8 . 2 280 Remark~:
1) "Differential Mechanical ~n~lysi~"
2) Only 1 laYer of slas~ fi~ers d = 0,11...0,2 mm 3) "Thermo Mechanical ~naly~
4) "Differential Scanning Calorimetry"

Claims

WE CLAIM:

1. A resin mixture which may be cured to form a polymeric resin having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, said resin mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group; and (b) a resin component consisting of at least one curable halogenated epoxy resin.

2. A resin mixture according to claim 1, wherein said 1-oxa-3-aza tetraline compound of, component (a) is derived from a phenolic compound, formaldehyde and an amine.

3. A resin mixture according to claim 1, wherein said 1-oxa-3-aza tetraline compound of component (a) is formally derived from a phenolic compound and an amine, one of said components being more than monofunctional.

4. A resin mixture according to claim 1, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a novolak.

5. A resin mixture according to claim 4, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a novolak having a degree of polymerization of 1.5 to 3.

6. A resin mixture according to claim 1, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from an aromatic amine.

7. A resin mixture according to claim 1, wherein said component (b) consists of one or several glycidyl ethers of halogenated phenols.

8. A resin mixture according to claim 1, wherein said component (b) consists of one or several glycidyl ethers of condensation products of halogenated phenols with aldehydes or ketones.

9. A resin mixture according to claim 1, wherein component (b) consists of at least one curable brominated epoxy resin.

10. A resin mixture according to claim 1, wherein the halogen content is less than 3 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

11. A resin mixture according to claim 10, wherein the halogen content is less than 2 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

12. A resin mixture according to claim 1, wherein the quantity of said component (b) is less than 50 percent by weight, based on the total weight of components (a) and (b).

13. A resin mixture according to claim 11, wherein the quantity of said component (b) is less than 30 percent by weight, based on the total weight of components (a) and (b).

14. A method for producing a polymeric resin having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, wherein a resin mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group; and (b) a resin component consisting of at least one curable halogenated epoxy resin;
is cured.

15. A method according to claim 14, wherein said resin mixture is cured in non-reinforced form.

16. A method according to claim 14, wherein said resin mixture is cured in reinforced form.

17. A method according to claim 14, wherein said resin mixture is cured at a temperature of above 100°C.

18. A method according to claim 14, wherein said resin mixture is tempered after curing.

l9. A method according to claim 18, wherein said resin mixture is tempered at a temperature of 180 to 250°C.

20. An electric insulating material having a flame resistance of cla6s V0 or V1 in the UL 94 Vertical Test, said material being the cured product of a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group; and (b) a resin component consisting of at least one curable halogenated epoxy resin.

21. An electric insulating material according to claim 20, said material further comprising at least one reinforcing means.

22. A supporting structure having a flame resistance of class V0 or V1 in the UL 94 Vertlcal Test, said supporting structure being the cured product of a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group; and (b) a resin component consisting of at least one curable halogenated epoxy resin.

23. A supporting structure according to claim 22, said structure further comprising at least one reinforcing means.

24. An adhesive which may be cured to form a polymeric resin having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, said adhesive being a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group; and (b) a resin component consisting of at least one curable halogenated epoxy resin.

25. A resin mixture which may be cured to form a polymeric resin having a flame resistance of class VO or V1 in the UL 94 Vertical Test, said resin mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (c) resin component consisting of at least one curable non-halogenated epoxy resin.

26. A resin mixture according to claim 25, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a phenolic compound, formaldehyde and an amine.

27. A resin mixture according to claim 25, wherein said 1-oxa-3-aza tetraline compound of component (a) is formally derived from a phenolic compound and a amine, one of said components being more than monofunctional.

28. A resin mixture according to claim 25, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a novolak.

29. A resin mixture according to claim 28, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a novolak having a degree of polymerization of 1.5 to 3.

30. A resin mixture according to claim 25, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from an aromatic amine.

31. A resin mixture according to claim 25, wherein said component (b) consists of one or several glycidyl ethers of halogenated phenols.

32. A resin mixture according to claim 25, wherein said component (b) consists of one or several glycidyl ethers of condensation products of halogenated phenols with aldehydes or ketones.

33. A resin mixture according to claim 25, wherein component (b) consists of at least one curable brominated epoxy resin.

34. A resin mixture according to claim 25, wherein the halogen content is less than 3 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

35. A resin mixture according to claim 34, wherein the halogen content is less than 2 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

36. A resin mixture according to claim 25, wherein the quantity of said component (b) is less than 50 percent by weight, based on the total weight of components (a) and (b).

37. A resin mixture according to claim 36, wherein the quantity of said component (b) is less than 30 percent by weight, based on the total weight of components (a) and (b).

38. A resin mixture according to claim 25, wherein the quantity of said component (c) is less than the quantity of said component (b) .

39. A method for producing a polymeric resin having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, wherein a resin mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (c) resin component consisting of at least one curable non-halogenated epoxy resin;
is cured.

40. A method according to claim 39, wherein said resin mixture is cured in non-reinforced form.

41. A method according to claim 39, wherein said resin mixture is cured in reinforced form.

42. A method according to claim 39, wherein said resin mixture is cured at a temperature of above 100°C.

43. A method according to claim 39, wherein said resin is tempered after curing.

44. A method according to claim 43, wherein said resin is tempered at a temperature of 180 to 250°C.

45. An electric insulating material having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, said material being the cured product of a mixture comprising:

(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (c) resin component consisting of at least one curable non-halogenated epoxy resin.

46. An electric insulating material according to claim 45, said material further comprising at least one reinforcing means.

47. A supporting structure having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said supporting structure being the cured product of a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (c) resin component consisting of at least one curable non-halogenated epoxy resin.

48. A supporting structure according to claim 47, said structure further comprising at least one reinforcing means.

49. An adhesive which may be cured to form a polymeric resin having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said adhesive being a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;

(b) a resin component consisting of at least one curable halogenated epoxy resin; and (c) resin component consisting of at least one curable non-halogenated epoxy resin.

50. A resin mixture which may be cured to form a polymeric resin having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, said resin mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (d) a curing agent for epoxy resins.

51. A resin mixture according to claim 50, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a phenolic compound, formaldehyde and an amine.

52. A resin mixture according to claim 50, wherein said 1-oxa-3-aza tetraline compound of component (a) is formally derived from a phenolic compound and an amine, one of said components being more than monofunctional.

53. A resin mixture according to claim 50, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a novolak.

54. A resin mixture according to claim 53, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a novolak having a degree of polymerization of 1.5 to 3.

55. A resin mixture according to claim 50, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from an aromatic amine.

56. A resin mixture according to claim 50, wherein said component (b) consists of one or several glycidyl ethers of halogenated phenols.

57. A resin mixture according to claim 50, wherein said component (b) consists of one or several glycidyl ethers of condensation products of halogenated phenols with aldehydes or ketones.

58. A resin mixture according to claim 50, wherein component (b) consists of at least one curable brominated epoxy resin.

59. A resin mixture according to claim 50, wherein the halogen content is less than 3 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

60. A resin mixture according to claim 59, wherein the halogen content is less than 2 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

61. A resin mixture according to claim 50, wherein the quantity of said component (b) is less than 50 percent by weight, based on the total weight of components (a) and (b)

62. A resin mixture according to claim 61, wherein the quantity of said component (b) is less than 30 percent by weight, based on the total weight of components (a) and (b).

63. A resin mixture according to claim 50, containing as component (d) one or several compounds selected from the group selected from polyvalent amines, polyvalent carboxylic acids, anhydrides of polyvalent carboxylic acids, dicyano diamide, and novolaks.

64. A resin mixture according to claim 63, wherein the quantity of said component (d) is less than 1.2 times the total equivalent quantity of said components (b) and (c).

65. A method for producing a polymeric resin having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, wherein a resin mixture comprising:
(a) a resin components consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group (b) a resin components consisting of at least one curable halogenated epoxy resin: and (d) a curing agent for epoxy resins;
is cured.

66. A method according to claim 65, wherein said resin is cured in non-reinforced form.

67. A method according to claim 65, wherein said resin is cured in reinforced form.

68. A method according to claim 65, wherein said resin is cured at a temperature of above 100°C.

69. A method according to claim 65, wherein said resin is tempered after curing.

70. A method according to claim 69, wherein said resin is tempered at a temperature of 180 to 250°C.

71. An electric insulating material having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, said material being the cured product of a mixture comprising:

(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (d) a curing agent for epoxy resins.

72. An electric insulating material according to claim 71, said material further comprising at least one reinforcing means.

73. A supporting structure having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said supporting structure being the cured product of a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (d) a curing agent for epoxy resins.

74. A supporting structure according to claim 73, said structure further comprising at least one reinforcing means.

75. An adhesive which may be cured to form a polymeric resin having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said adhesive being a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin; and (d) a curing agent for epoxy resins.

76. A resin mixture which may be cured to form a polymeric resin having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said resin mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin;
(c) resin component consisting of at least one curable non-halogenated epoxy resin; and (d) a curing agent for epoxy resins.

77. A resin mixture according to claim 76, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a phenolic compound, formaldehyde and an amine.

78. A resin mixture according to claim 76, wherein said 1-oxa-3-aza tetraline compound of component (a) is formally derived from a phenolic compound and an amine, one of said components being more than monofunctional.

79. A resin mixture according to claim 76, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from as novolak.

80. A resin mixture according to claim 79, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from a novolak having a degree of polymerization of 1.5 to 3.

81. A resin mixture according to claim 76, wherein said 1-oxa-3-aza tetraline compound of component (a) is derived from an aromatic amine.

82. A resin mixture according to claim 76, wherein said component (b) consists of one or several glycidyl ethers of halogenated phenols.

83. A resin mixture according to claim 76, wherein said component (b) consists of one or several glycidyl ethers of condensation products of halogenated phenols with aldehydes or ketones.

84. A resin mixture according to claim 76, wherein component (b) consists of at least one curable brominated epoxy resin.

85. A resin mixture according to claim 76, wherein the halogen content is less than 3 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

86. A resin mixture according to claim 85, wherein the halogen content is less than 2 gram equivalents, based on 1 kilogram of the total weight of components (a) and (b).

87. A resin mixture according to claim 76, wherein the quantity of said component (b) is less than 50 percent by weight, based on the total weight of components (a) and (b).

88. A resin mixture according to claim 87, wherein the quantity of said component (b) is less than 30 percent by weight, based on the total weight of components (a) and (b).

89. A resin mixture according to claim 76, wherein the quantity of said component (c) is less than the quantity of said component (b).

90. A resin mixture according to claim 76, containing as component (d) one or several compounds selected from the group selected from polyvalent amines, polyvalent carboxylic acids, anhydrides of polyvalent carboxylic acids, dicyano diamide, and novolaks.

91. A resin mixture according to claim 90, wherein the quantity of said component (d) is less than 1.2 times the total equivalent quantity of said components (b) and (c).

92. A method for producing a polymeric resin having a flame resistance of class V0 or V1 in the UL 94 Vertical Test, wherein a resin mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin;
(c) resin, component consisting of at least one curable non-halogenated epoxy resin: and (d) a curing agent for epoxy resins:
is cured.

93. A method according to claim 92, wherein said resin mixture is cured in non-reinforced form.

94. A method according to claim 92, wherein said resin mixture is cured in reinforced form.

95. A method according to claim 92, wherein said resin mixture is cured at a temperature of above 100°C.

96. A method according to claim 92, wherein said resin mixture is tempered after curing.

97. A method according to claim 96, wherein said resin mixture is tempered at a temperature of 180 to 250°C.

98. An electric insulating material having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said material being the cured product of a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin;
(c) resin component consisting of at least one curable non-halogenated epoxy resin; and (d) a curing agent for epoxy resins.

99. An electric insulating material according to claim 98, said material further comprising at least one reinforcing means.

100. A supporting structure having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said supporting structure being the cured product of a mixture comprising:
(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin;
(c) resin component consisting of at least one curable non-halogenated epoxy resin; and (d) a curing agent for epoxy resins.

101. An adhesive which may be cured to form a polymeric resin having a flame resistance of class V? or V1 in the UL 94 Vertical Test, said adhesive being a mixture comprising:

(a) a resin component consisting of at least one compound containing at least one thermically curable 1-oxa-3-aza tetraline group;
(b) a resin component consisting of at least one curable halogenated epoxy resin;
(c) resin component consisting of at least one curable non-halogenated epoxy resin; and (d) a curing agent for epoxy resins.

102. An adhesive comprising a polymeric resin which is the cured product of a mixture comprising:
(a) a component consisting of at least one thermically curable 1-oxa-3-aza tetraline groups containing compound;
(b) a component consisting of at least one curable halogenated epoxy resin;
(c) a component consisting of at least one curable non-halogenated epoxy resin; and (d) a curing agent for epoxy resins.