AU636226B2 - Resins which may be cured to form polymeric resins which are difficultly inflammable and resistant to high temperatures, method for preparing and use of said polymeric resins - Google Patents
Resins which may be cured to form polymeric resins which are difficultly inflammable and resistant to high temperatures, method for preparing and use of said polymeric resins Download PDFInfo
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- AU636226B2 AU636226B2 AU77213/91A AU7721391A AU636226B2 AU 636226 B2 AU636226 B2 AU 636226B2 AU 77213/91 A AU77213/91 A AU 77213/91A AU 7721391 A AU7721391 A AU 7721391A AU 636226 B2 AU636226 B2 AU 636226B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
636226
AUSTRALIA
Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
Applicant(s): GURIT-ESSEX AG Actual Inventor(s): Br 'rt Herbert Schreiber Dr Gunter Burkart Bruno Knaus PATENT ATTORNEY SERVICES 26 Ellingworth Parade Box Hill Victoria 3128 Australia Address for Service: Title: RESINS WHICH MAY BE CURED TO FORM POLYMERIC RESINS WHICH ARE DIFFICULTLY INFLAMMABLE AND RESISTANT TO HIGH TEMPERATURES, METHOD FOR PREPARING AND USE OF SAID POLYMERIC RESINS Associated Provisional Applications: No(s).: The following statement is a full description of this invention, including the best method of performing it known to me/us:- -1- RESINS WHICH MAY BE CURED TO FORM POLYMERIC RESINS WHICH ARE DIFFICULTLY INFLAMMABLE AND RESISTANT TO HIGH TEMPERATURES, METHOD FOR PREPARING AND USE OF SAID POLYMERIC RESINS FIELD OF THE INVENTION
S
'3 This invention refers to resins 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.
S .o BACKGROUND OF THE INVENTION **see: Jd Compounds containing l-oxa-3-aza tetraline groups and their 0* S 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 is known which 15 may be cured to form polymeric resins which are difficultly inflammable and resistant to high temperatures. Said resin is at least partially a mixture of: a resin component comprising or consisting of at least one thermically curable l-oxa-3-aza tetraline groups containing compound; and of a flame retardant which is not miscible with resin component 2 and optionally also contains at least one curable epoxy compound.
It is true that by curing said known resin, products which are difficultly inflammable and resistant to high temperatures may be obtained. However, their properties are still not sufficient for many uses, since the mechanical and electrical properties are deteriorated by the flame retardant additive SUMMARY OF THE INVENTION O0 An object of the present invention is to eliminate the dis- 1 advantages of the prior art described above, and to further improve the behavior in fire of oxazene resins without deteriorating their other properties.
According to the present invention, this object is met by a resin which may be cured to form a polymeric resin which is IT" difficultly inflammable and resistant to high temperatures, said resin comprising a'mixtue of: a component consisting of at least one thermically curable 1 oxa-3-aza tetraline groups containing compound; '20 a component consisting of at least one curable halogenated epoxy resin; optionally a component consisting of at least one curable nonhalogenated epoxy resin; and/or optionally a curing agent for epoxy resins.
S- 3 PREFERRED EMBODIMENTS OF THE INVENTION The compounds containing l-oxa-3-aza tetraline groups of component are obtained, for example, from phenols by reaction with formaldehyde and an amine, approximately according to formula
OH
2 H20 0 S+ 2 CHO Hn- R'
(A)
0S* S
R.
l-oxa-3-aza tetraline group s" For example, R is hydrogen, halogen, alkyl or alkoxy, and R' is an aliphatic or aromatic group.
However, the compounds containing l-oxa-3-aza tetraline groups of component can also be prepared by other methods resulting into similar products.
In contrast to other known condensation reactions of phenols, amines and formaldehyde, in the reaction outlined above S phenolic OH-groups are consumed. It is thereby possible, ac- °1 cording to the formula hereinabove, to determine the amount S0" of the synthesized l-oxa-3-aza tetraline groups from the analytic determination of the said OH-groups in the reaction mixture.
Prepolymers of l-oxa-3-aza tetraline groups containing compounds are also useful for preparing said oxazene resins. Since some of the l-oxa-3-aza tetraline groups may react during polymerization, these prepolymers may contain a smaller number of -4 said l-oxa-3-aza tetraline groups than provided by the monomers used to form such prepolymers. However, it is essential that the intermediately formed or hypothetic monomer reaction product does in fact contain l-oxa-3-aza tetraline groups. This can easily be calculated by a person skilled in the art from the functionality. An l-oxa-3-aza tetraline compound, or its prepolymer, useful in accordance with the present invention is, for example, formed if the molar ratio is kept within the limits defined in the abovementioned publication CH-A5-606,169.
Phenol or phenol derivatives as well as amines and formaldehyde are used as starting or basic materials for preparing the oxazene resin.
S
Preferably, for the present invention, l-oxa-3-aza tetraline groups containing compounds are used which are formally derived from a phenol and an amine, one of said components being more than monofunctional.
ooeo S. Examples of phenols which can be used are: 0. 0 Monovalent phenols, such as phenol, m- and p-cresol, m- and p-ethyl phenol, m- and p-isopropyl phenol, m- and p-isopropyloxy phenol, m- and p-chloro phenol, and beta-naphthol.
?ara- and meta-substituted phenols are preferred, since they do not include any blocked reactive positions. Also preferred are the phenols which are not alkyl substituted and not alkyloxy substituted, respectively.
Bivalent phenols, such as 4,4'-dihydroxydiphenyl methane, 3,3'-dihydroxydiphenyl methane, 2,2'-bis-(4-hydroxyphenyl) propane, 4,4'-dibydroxy stilbene, hydroquinone, and resorcin.
5 Low-condensed phenolic formaldehyde novolak resins, eventually mixed with a phenol.
Examples of amines which are particularly useful are: Aniline, phenylene diamine, benzidine, diaminodiphenyl methane, 2,2'-bis-(aminophenyl) propane, cyclohexylamine, ethylenediamine and propylenediamine, in particular p-phenylenediamine and 4,4'-diaminodiphenyl methane, aromatic amines being preferred.
Also particularly useful are l-oxa-3-aza tetraline com- 9 10. pounds which are derived from a novolak and an aromatic amine, O preferably from a novolak having a degree of polymerization of -about 2 and of aniline, or from phenol and an aromatic diamine.
Preferably, the second component 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 halogenated phenols with aldehydes or ketones; or one or several glycidyl ethers of halogenated novolaks.
Particularly useful are the glycidyl ethers of halogenated bisphenol A or of halogenated bisphenol F, in particular tetra- *0 bromo bisphenol A or tetrabromo bisphenol F, as well as brominated novolaks.
Preferably, the halogenated epoxy resin of component is a brominated epoxy resin.
Such brominated epoxy resins are known and commercially available. Also, they were already proposed, as sole component, for preparing difficultly inflammable polymeric resins. However, said polymeric resins show the following essential draw- 'backs: 6 They have glass transition temperatures which are too low.
In the case of combustion, they produce considerable quantities of the highly toxic carbonyldibromide, due to their high bromine content.
They are expensive.
a.
0 a 0 a a a a *0 ~r Product No. 1 (Trade Name: 511-A 80" of Brominated epoxy resin of the tone solution.
Epoxide equivalent weight 1): Viscosity (25 0
C):
Non-volatiles: Solvent: Color according to Gardner, maximum: Bromine content 1): Flash point The Dow Chemical Company): bisphenol-A type in an ace- 445...520 1000...4000 80+1 Acetone mPa-s percent by weight 19...21 63 percent by weight
OC
Product No. 2 (Trade Name: 511-EK 80" of The Dow Chemical Company): Brominated epoxy resin of the bisphenol-A type in a methyl ethyl ketone solution.
Epoxide equivalent weight 445...522 Viscosity (25 0 1000...4000 mPa-s Non-volatiles: 80+1 percent by weigh Solvent: Methyl ethyl ketone Color according to Gardner, maximum: 9 Bromine content 19...21 percent by weigh Flash point 52 °C t t i 7
S.
4 6 4 6 4r 6 a, 5 0 066 .I 46 U 6 a0 6 Product No. 3 (Trade Name: 512-A 80" of Brominated epoxy resin of the tone solution.
Epoxide equivalent weight 1): Viscosity (25 0
C):
Non-volatiles: Solvent: Color according to Gardner, maximum: Bromine content 1): Flash point The Dow Chemical Company): bisphenol-A type in an ace- 480...560 700...2500 80±1 Acetone mPa s percent by weight 21...22,5 56 percent by weight
OC
Product No. 4 (Trade Name: 512-EK 75" of The Dow Chemical Company): Brominated epoxy resin of the bisphenol-A type in a methyl ethyl ketone solution.
Epoxide equivalent weight 480...560 Viscosity (25 0 500...1500 mPa-s Non-volatiles: 75+1 percent by weigh,t Solvent: Color according to Gardner, maximum: Bromine content 1): Flash point Methyl ethyl ketone 3 21...22,5 <-2 percent by weight
OC
Product No. (Trade Name: 512-EK 80" of The Dow Chemical Company): Brominated epoxy resin of the bisphenol-A type in a methyl ethyl ketone solution.
Epoxide equivalent weight 480...560 Viscosity (25 0 1000...3500 mPa.s Non-volatiles: 80+1 percent by weight Solvent: Methyl ethyl ketone -8 Color according to Gardner, maximum: Bromine content 1): Flash point 21...22,5- 52 percent by weight oc Product No. 6 (Trade Name: 521-A 80" of Brominated epoxy resin of the tone solution.
Epoxide equivalent weight 1): 01. Viscosity (250C): Non-volatiles: Solvent: S' Color according to Gardner, maximum: Bromine content 1): Flash point The Dow Chemical Company): bisphenol-A type in an ace- 430...475 1000...4500 80+1 Acetone mPa-s percent by weight 19...22 63 percent by weight oc Product No. 7 (Trade Name: 542" of The Dow Chemical Brominated epoxy resin of the bisphenol-A Epoxide equivalent weight 305...355 Softening point according to Durran: 50,5...62,5 Bromine content: 44...49 Flash point 199 Company): type.
oc pe]
OC
rcent by weight Product No. 8 (Trade Name: 566-A 80" of Brominated epoxy resin of the tone solution.
Epoxide equivalent weight 1): Viscosity (25°C): Non-volatiles: The Dow Chemical Company): bisphenol-A type in an ace- 410...450 800...4000 mPa-s 80+1 percent by weight 9 Solvent: Color according to Gardner, maximum: Bromine content 1): Flash point Acetone 18...20 <2 percent by weight oc 00 1 S. 0
I
S
S.
S.
S
Product No. 9 (Trade Name: "QUATREX 6410" of The Dow Chemical Company): Brominated epoxy resin of the bisphenol-A type.
Epoxide equivalent weight 450 Softening point: 80 °C Viscosity (150 0 0,0180 m2.s- 1 Hydrolyzable chloride: <150 ppm Volatiles: <0,25 percent by weight Bromine content: 47...51 percent by weight Glass transition temperature after phenolic curing: 175
OS.
0
S
S.
S
S.
1) Based on the solids content Preferably, the halogen content is less than 3 gram equivalents, in particular less than 2 equivalents, based on 1 kilogram 20 of the total weight of the abovementioned components to Consequently, in resins containing a brominated ecpoxy resin as component the bromine content is preferably less than 24 percent by weight, in particular less than 16 percent by weight, based on the total weight of the resin. Even with bromine contents as low as 7.5, 2.5, and 1 percent by weight, respectively, flame resistant can be obtained.
NT
0 10 Preferably, the quantity of component is less than percent by weight, in particular less than 30 percent by weight, based on the total weight of the resin (component component However, flame resistant resins are already obtained 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 based on the total weight of the resin.
The fact that the advantages described hereafter may be obtained with such small quantities of the component in particular of a brominated epoxy resin, was highly surprising to a
C
p erson skilled in the art.
It is a particular advantage that beside an essentially improved thermic behavior in combination with excellent electrical properties which will be explained hereafter in detail in the case of combustion they produce only small quantities of toxic compounds, and that only a small quantity of the expensive component must be used.
The mixture according to the invention may also comprise a component comprising or consisting of at least one non-halogenated epoxy resin. Advantageously, the quantity of said component is less than the quantity of component and preferably less than half the quantity of component e Such suitable epoxy resins are in particular monofunctional oe or multifunctional epoxy compounds which can be cured thermically, catalyticly or by means of a curing agent.
The mixture according to the invention may also comprise as component a curing agent for epoxy resins. Polyvalent amines, polyvelent carboxylic acids and their anhydrides, dicyano diamide, as well as novolaks are particularly useful as such curing agents.
lOa Preferably, the quantity of the component is less than 1.2 times the total equivalent quantity of the components (b) and 10 o o° *o go go oo o.l 11 Suitable epoxy compounds and curing agent are, 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 and Kris Neville, Handbook of Epoxy Resins, McGraw-Hill Book Company, New York/San Francisco/Toronto/ London.
By thermically curing the abovementioned curable resins,\at a 1t, temperature of above 100 OC, in particular at a temperature of 06000: 140 to 220 OC, polymeric resins which are difficultly inflammaanv c ble resistant to high temperatures ga-J .i-j T can be obtained.
Surprisingly, the properties of the polymeric resins cured as explained above can still be considerably improved by a thermic aftertreatment. Thus, for example, by tempering them for 24 hours at a temperature of 220 OC, the glass transition temperao 0 ture rises up to more than 280 oC.
Advantageously, the cured polymeric resins are subject to said thermic aftertreatment at a temperature of 180 to 250 OC, and preferably at a temperature of 200 to 230 OC. The duration of said tempering depends on the temperature. The following standard values may serve as a basis; however, the durations can
S.
be extended at will without deterioration of the polymeric resins: Curing: 4 hours at 180 OC; or 2 hours at 200 OC.
12 Tempering: 24 hours at 220 oC.
Also, these durations can be proportionally combined at will.
For example, the following tempering cycle has proved its value: 30 minutes/200 OC 30 minutes/220 OC 30 minutes/230 OC minutes/250 oC.
The properties of the polymeric resins produced as described above can be tailored for certain applications by addition of usual additives. The following additives are of particular importance: reinforcement fibers, such as glass, quartz, carbon, mineral and synthetic fibers, in the usual forms of short fibers, staple fibers, threads, fabrics or mats; plasticizers, especially phosphorous compounds; carbon black or graphite; fillers; dyestuffs; micro hollow spheres; metal powder; catalysts; and flame retardants, in particular the following groups of compounds, and compounds, respectively: aluminium hydroxide; *3 hydrated calcium magnesium carbonate; magnesium hydroxide; elemental red phosphorous; oxygen acids of phosphorous; inorganic salts of oxygen acids of phosphorous; organic salts of oxygen acids of phosphorous; polyphosphates; boric acid; salts of boric acids.
13 The methods known for processing thermically curable phenol formaldehyde resins or EP resins, such as hot-pressing of prepregs, SMC (Sheet Molding Compound); or molding of molding compounds, casting, filament winding, vacuum impregnating, may be used for processing 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 invention, and which are difficultly inflammable and resistant to high temperatures, are particularly suitable for the following 410 uses: Sa *0 S as electric insulating materials, in particular for printed circuit boards; for supporting structures, in particular in aircraft constructions; wherever resins which are flame-resistant or resistant to high temperatures are to be used; as adhesives.
S
EXAMPLES
1. Starting materials The following starting materials are used in the following examples: 14
S
S
V
S.
.5 S* e* S S. S S S
S
Component Oxazene resin 1 Reaction product of phenol with aniline and formaldehyde in a molar ratio of 1:1:2, having the structural formula: Oxazene resin 2 Reaction product of 1 mole (2 equivalents) of the novolak obtained by reacting 2 moles of phenol and 1 mole of formaldehyde, with 2 moles of aniline and with 4 moles of formaldehyde, having the the following average composition: 555555
S
So
S
S Oxazene resin 3 Reaction product of 4,4'-diamino-diphenylmethane with phenol and formaldehyde in a molar ratio of 1:2:4, having the structural formula: 15 N 0 CH2 Component Brominated epoxy resin 1 "D.E.R 542" of The Dow Chemical Company Bromine content, based on solids: 44...49 percent by weight 0 Brominated epoxy resin 2 "Quatrex 6410" of The Dow Chemical Company Bromine content, based on solids: 47...51 percent by weight SReinforcing material Glass cloth "Type 90085" of Interglas-Textil GmbH go *Surface density: 108 g/m 2 Number of threads/cm: 24x24 Epoxy silane finish 0 2. Preparation of samples The components specified in Table 1 were mixed under reduced pressure at 100 bis 130 oC. Then, the samples for the thermal analysis were withdrawn. The remainder was soaked up, with or without glass cloth, between teflonized glass plates and cured in an circulating air oven for 2 hours at 200 oC.
16 The term "Ref." means the internal reference number of Applicant.
3. Flame-resistance test The flame-resistance test was made according to UL Specification 94 (Vertical Test), abreviated: "UL 94" JUrgen Troitzsch, Brandverhalten von Kunststoffen (1982 Munich/Vienna ISBN 3-446-13391-7), pages 396 to 399).
The results are compiled in Table 1.
S
It was surprising that Class UL-94-VO can already be obtained by an addition of 20 percent by weight of brominated epoxy resin, for glass cloth reinforced samples already by an addition of 10 percent by weight.
4. Mechanical properties
S
The mechanical properties and the glass transition temperature T. (also called "glass temperature") were determined, with or without tempering, by means of DCS ("Differential Scanning Calorimetry"), DMA ("Differential Mechanical Analysis"), and TMA ("Thermo Mechanical Analysis").
The results are comp.iled in Table 2.
It was extremely surprising that the rise in the glass transition temperature obtainable by a tempering is associated with an essentially reduced drop of the E' module at this temperature (cf. in particular: Sample 4, Ref. Kb71-G).
17 Table 1: Composition of samples (parts by weight) Flame-resistance test according to UL 94 Sample <(-------Composition <-Flame resistance UL 94-> Ref.
A/1 A/2 A/3 B/1 B/2 Glass
R
Ilayers Th ick-.
ness nun Duration of combustion s 1st 2nd ignition Class p.
0 0' 0 0 0 0 S. 0 *0 0*0 00
*S.
5 2.5 1 0,80 9 0,92 0,80 9 0,90 1,00 1 ,03 1,05 1 ,07 1,03 1 ,04 9 1,04 9 1,02 9 1,02 1,00 4,0 2,6 1,7 1,5 0,0 0,0 0,0 11,7 6,7 1,7 10 13 38 3 4,8 3,0 0,7 0,5 2, 0,3 0,0 14 7,3 3,7 3 10 10 2 Kb7 0 Kb7O-G Kb7 1 Kb7l-G 17-1 17-3 17-2 17-4 17-6 17-5 17-9 17-8 El E2 0 i 97,5 99 Comparative test 100 9 1,02 Burns up to top 1- 17-7 18 Tqh e2: Mecharnical Iproportieg semple Curing/ <---Strength---> TMA DC5 Ref.
No. temper- Bending E module Thicki ng h/OC strength N/mm 2 nes
MM
2)
V'
80 0
E,
1 6 0 Gpa G*& N/mm 2 S S
S
S
5005*6
S
S.
SO
0S
S.
5 0*S *6 OSe 1 2/200 2 2/200 3 2/200 +24/220 +72/220' 4 2/200 2/220 +24/220 522± 14 118±5 1 03+2 1 112+29 495+14 23'500 11,800 14,800 14,400 22,300 4.8 0.91 2.7 0.85 5.8 5.7 5.4 0.91 3.0 4.4 8.5 1.2 2.4 4.9 4.7 1.6 8.2 182 171 WbO 178 Kb71.
Kb71-G 5 6 7 a 9 10 2.81 17-1 179 17-3 184 17-2 162 17-4 158 17-6 156 17-5
S
*5S505 0 5e54 S. S
S.
S S *SS 5
S
555.5.
0 55 S 5* S *4 20 Remarks; 1) "Differentia Mechanieal Analysis" 2) Orly 1 layer of glass fibers d .2 mm.n 3) "Thermo Mechani~cal Analysis" 4) "D~ifferential Scanninc Calorimetry"
Claims (17)
1. A resin which may be cured to form a polymeric resin which is difficultly inflammable and resistant to high tem- peratures, said resin comprising a mixture of: a component consisting of at least one thermically curable 1-oxa-3-aza tetraline groups containing com- pound; a component consisting of at least one curable halogen- ated epoxy resin; optionally a component consisting of at least one curable non- halogenated epoxy resin; and/or optionally a curing agent for epoxy resins.
2. A resin according to claim 1, wherein said l-oxa-3-aza tetraline compound of component is derived from a phenolic compound, formaldehyde and an amine. S
3. A resin according to claim 1 or 2, wherein said 1-oxa- 3-aza tetraline compound of component is formally derived from a phenolic compound and an amine, one of said components being more than monofunctional.
4. A resin according toAone or =everal of claims 1 to 3, wherein said l-oxa-3-aza tetraline compound of component is derived from a novolak. 20 A resin according to claim 4, wherein said l-oxa-3-aza tetraline compound of component is derived from a novolak having a degree of polymerization of 1.5 to 3 cQ\- o.N
6. A resin according toAone oi seve-1 of claims 1 to wherein said l-oxa-3-aza tetraline compound of component is derived fromAan aromatic amine.
7. A resin according tohone us .avera1 of claims 1 to 6, wherein said component consists of one or several glycidyl ethers of halogenated phenols. a 0
8. A resin according toione or see-- of claims 1 to 6, wherein said component consists of one or several glycidyl ethers of condensation products of halogenated phenols with aldehydes or ketones.
9. A resin according to one rsevr of claims 1 to 8, ,*1 5 wherein component consists of at least one curable bromin- ated epoxy resin.
10. A resin according to one of claims 1 to 9, wherein the halogen content is less than 3 gram equivalents, and preferably less than 2 gram equivalents, based on 1 kilo- gram of the total weight of components and 21
11. A resin accordi.ng--toone-ao=se; wa of claims 1 to wherein the quantity of said component is less than 50 per- cent by weight, and preferably less than 30 percent by weight, based on the total weight of components and
12. A resin according toxone o leverd of claims 1 to 11, wherein the quantity of said component is less than the quantity of said component ca
13. A resin according toAone wevrl of claims 1 to 12, containing as component one or several compounds selected S10: from the group selected from polyvalent amines, polyvalent -4 carboxylic acids, anhydrides of polyvalent carboxylic acids, dicyano diamide, and novolaks.
14. A resin according to claim 13, wherein the quantity of said component is less than 1.2 times the total equivalent quantity of said components and A method for producing polymeric resins which are dif- ficultly inflammable and resistant to high temperatures, wherein a resin according to one ori evaea of claims 1 to 14, *A in non-reinforced or reinforced form, is cured, or is cured and thereafter tempered.
16. A method according to claim 15, wherein said resin is cured at a temperature of above 100 OC.
17. A method according to claim 15, wherein said resin is tempered at a temperature of 180 to 250°C.
18. An electric insulating material comprising a polymeric resin according to any one of claims 15 to 17.
19. A supporting structure comprising a polymeric resin according to any one of claims 15 to 17. An adhesive comprising a resin according to any one of claims 1 to 14. .10 Dated this 12th Day of February, 1993 S PATENT ATTORNEY SERVICES Attorneys for GURIT-ESSEX AG 1 se S *0e S C., -r Q I I 23 ABSTRACT OF THE DISCLOSURE Polymeric resins which are difficultly inflammable and/or resistant to high temperatures are obtained by curing a curable resin which comprises a mixture of: a component consisting of at least one thermically curable 1-oxa-3-aza tetraline groups containing com- pound; a component consisting of at least one curable halogen- ated epoxy resin; and optionally 6S 'n* *6 ".1Q a component consisting of at least one curable non- ha.ogenated epoxy resin; and/or optionally ee a curing agent for epoxy resins. By tempering them, the glass transition temperature and the mechanical properties car be further improved. The obtained polymeric resins may be used as follows: as electric insulating materials, in particular for printed cir- cuit boards; in aircraft constructions, also for supporting structures; adhesives; and moreover wherever resins which are flame-resistant are to be used. oS
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4016296A DE4016296C1 (en) | 1990-05-21 | 1990-05-21 | Flame retardant thermosetting adhesive for metals etc. - comprises oxa:aza:tetralin, halogenated epoxy] resins and opt. additives |
| DE4016296 | 1990-05-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU7721391A AU7721391A (en) | 1991-11-21 |
| AU636226B2 true AU636226B2 (en) | 1993-04-22 |
Family
ID=6406865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU77213/91A Expired AU636226B2 (en) | 1990-05-21 | 1991-05-21 | Resins which may be cured to form polymeric resins which are difficultly inflammable and resistant to high temperatures, method for preparing and use of said polymeric resins |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0458739A3 (en) |
| JP (1) | JP3203385B2 (en) |
| KR (1) | KR0166377B1 (en) |
| AU (1) | AU636226B2 (en) |
| CA (1) | CA2042840C (en) |
| CS (1) | CS145891A2 (en) |
| DE (1) | DE4016296C1 (en) |
| ZA (1) | ZA913434B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0493310A1 (en) * | 1990-12-21 | 1992-07-01 | Gurit-Essex AG | Curable resin compositions having flame resistant properties in the cured state and use thereof |
| CN1058738C (en) * | 1994-07-29 | 2000-11-22 | 四川联合大学 | Open-loop polymerized phenolic resin and relevant composite fibre-reinforced material |
| JP3543866B2 (en) * | 1995-02-28 | 2004-07-21 | 日立化成工業株式会社 | Friction material and method of manufacturing the same |
| JPH09157496A (en) * | 1995-12-06 | 1997-06-17 | Hitachi Chem Co Ltd | Thermosetting resin composition, cured product therefrom, prepreg and metallic foil-laminated plate using the same |
| JP3487083B2 (en) * | 1996-02-09 | 2004-01-13 | 日立化成工業株式会社 | Thermosetting resin composition and cured product thereof |
| DE10309617A1 (en) * | 2003-03-05 | 2004-09-23 | Siemens Ag | Workpiece carrier for holding workpieces |
| US7157509B2 (en) * | 2003-06-27 | 2007-01-02 | Henkel Corporation | Curable compositions |
| US20050042961A1 (en) | 2003-08-18 | 2005-02-24 | Henkel Loctite Corporation | Curable compositions for advanced processes, and products made therefrom |
| JP2004156045A (en) * | 2003-12-22 | 2004-06-03 | Hitachi Chem Co Ltd | Friction material |
| DE102004046744B4 (en) | 2004-09-27 | 2007-05-24 | Atotech Deutschland Gmbh | Process for transferring powders and powder coatings to substrates and use for the production of printed circuit boards and solar cells |
| DE102004046745B4 (en) * | 2004-09-27 | 2008-04-24 | Atotech Deutschland Gmbh | Process for the solvent-free production of a fiber-reinforced, resin-coated film and use thereof |
| TWI374137B (en) * | 2004-09-28 | 2012-10-11 | Huntsman Adv Mat Switzerland | Organic compounds |
| US7649060B2 (en) | 2005-12-02 | 2010-01-19 | Henkel Corporation | Curable compositions |
| DE102006017891A1 (en) | 2006-04-13 | 2007-10-25 | Hexion Specialty Chemicals Gmbh | resin dispersion |
| EP2070984A1 (en) | 2007-12-12 | 2009-06-17 | Hexion Specialty Chemicals Research Belgium S.A. | Epoxy-phenolic resins co-dispersions |
| CN101952262B (en) | 2008-02-21 | 2012-07-18 | 亨斯迈先进材料美国有限责任公司 | Halogen-free benzoxazine based curable compositions for high TG applications |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH579113A5 (en) * | 1972-05-09 | 1976-08-31 | Micafil Ag | |
| ES414518A1 (en) * | 1972-05-09 | 1976-02-01 | Sued West Chemie Gmbh | Procedure for the preparation of synthetic materials. (Machine-translation by Google Translate, not legally binding) |
| DE3433851A1 (en) * | 1984-09-14 | 1986-03-27 | Gurit-Essex, Freienbach | CHEMICALLY CURABLE RESINS FROM COMPOUNDS CONTAINING 1-OXA-3-AZA-TETRALINE GROUPS AND CYCLOALIPHATIC EPOXY RESINS, METHOD FOR THE PRODUCTION AND CURING THEREOF AND THE USE OF SUCH RESINS |
| ATE135724T1 (en) * | 1988-07-18 | 1996-04-15 | Gurit Essex Ag | RESINS HARDENABLE TO FLAMMABLE AND HIGH TEMPERATURE RESISTANT PLASTIC MATERIALS AND METHOD FOR THE PRODUCTION THEREOF |
-
1990
- 1990-05-21 DE DE4016296A patent/DE4016296C1/en not_active Expired - Lifetime
-
1991
- 1991-04-26 EP EP19910810319 patent/EP0458739A3/en active Pending
- 1991-05-07 ZA ZA913434A patent/ZA913434B/en unknown
- 1991-05-17 CA CA002042840A patent/CA2042840C/en not_active Expired - Lifetime
- 1991-05-17 CS CS911458A patent/CS145891A2/en unknown
- 1991-05-20 KR KR1019910008163A patent/KR0166377B1/en not_active IP Right Cessation
- 1991-05-20 JP JP11485091A patent/JP3203385B2/en not_active Expired - Lifetime
- 1991-05-21 AU AU77213/91A patent/AU636226B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| KR0166377B1 (en) | 1999-03-20 |
| JPH04227922A (en) | 1992-08-18 |
| CS145891A2 (en) | 1991-12-17 |
| EP0458739A3 (en) | 1993-09-01 |
| EP0458739A2 (en) | 1991-11-27 |
| DE4016296C1 (en) | 1991-09-05 |
| JP3203385B2 (en) | 2001-08-27 |
| KR910020104A (en) | 1991-12-19 |
| AU7721391A (en) | 1991-11-21 |
| CA2042840A1 (en) | 1991-11-22 |
| CA2042840C (en) | 1996-11-26 |
| ZA913434B (en) | 1992-02-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PC | Assignment registered |
Owner name: VANTICO AG Free format text: FORMER OWNER WAS: CIBA SPECIALTY CHEMICALS HOLDING INC. |