CA2158336A1 - Flame retardant polyamides - Google Patents
Flame retardant polyamidesInfo
- Publication number
- CA2158336A1 CA2158336A1 CA 2158336 CA2158336A CA2158336A1 CA 2158336 A1 CA2158336 A1 CA 2158336A1 CA 2158336 CA2158336 CA 2158336 CA 2158336 A CA2158336 A CA 2158336A CA 2158336 A1 CA2158336 A1 CA 2158336A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- polyamide
- melamine
- phenol
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- 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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Flame retardant polyamide are provided which contain melamine as the flame retardant and a phenolic-aldehyde resin as a melamine compatibilizer and volatility control agent during subsequent compounding and molding of the compositions. Such compositions have a good fire rating and retain their physical and electrical properties.
Description
O WO 94/21723 2 l S 8 ~ 3 6 PCT/US94/02844 TITLE
FLAME RETARDANT POLYAMIDES
BACKCROUND OF THE rNVE~TlON
This invention relates to flame retardant polyamide compositions and more particularly to such compositions cont~ining a combination of melamine and phenol-aldehyde resins.
The use of melamine and melamine derivatives such as melamine cyanurate as flame retardant agents for polyamides has been known for many years (U.S. Patent 3,660,344 and U.S. Patent Re 30,402). In the case of polyamide 6.6, which is specifically used for its better thermal aging properties versus polyamide 6, the use of melamine as the flame retardant of choice has not been widely used commercially due to the fact that its volatility can lead to large amounts of white mold deposit and as previously noted (U.S. Patent 4,525,505) melamine can bleed from molded parts under various sim~ ted use conditions~ The alternative to melamine has been the use of melamine derivatives or its condensation products such as melamine cyanurate; but, although these have presented solutions to the melamine blooming issues, they have proved difficult to scale-up to typical commercial processes without some loss of fl~mm~ility control.
The volatility rate of melamine from polyamides containing it is comparable to melamine itself because of the incompatibility of melamine with poly~mides It has now been found that phenol-aldehyde resins, such as phenol-formaldehyde resins sold under the name novolac, reduce and in some cases elimin~te mold deposit and humid blooming of the melamine during compounding and molding of the polyamide compositions.
Polyamide compositions cont~ining a combination of melamine and a phenol-aldehyde resin according to the invention have the advantages of having a flame resistant rating of VO under E~94 and retaining their physical and electrical properties.
According to the present invention, provided is a flame retardant polyamide composition which comprises:
(a) 45-95% by weight of a polyamide, preferably 65-95% by weight, and most preferably 75-90% by weight;
(b) 2-30% by weight of mel~mine, preferably 2-15~ by weight, and most preferably 5-15% by weight; and ~15~36 (c) 2-30~o by weight of a phenol-aldehyde resin, preferably 2-15~ by weight, and most preferably 5-15% by weight; and optionally (d) 0-50% by weight, preferably 0-30~o by weight, of at least one of a reinforcing agent or filler. ?
When a reinforcing agent and/or filler are used, they are preferably used at a concentration of 10-30~o by weight.
Polyamides useful in the compositions of this invention are well known in the art and embrace those semi-crystalline and amorphous polymers having a molecular weight of at least 5000 and commonly referred to as nylons. Suitable polyamides include those described in U.S. Patent Nos. 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 3,312,966, 2,512,606, and 3,393,210. The polyamide can be produced by condensation of equimolar amounts of a saturated dicarboxylic acid cont~ininE from 4 to 12 carbon atoms with a diamine, in which the r1i~mine contains from 4 to 14 carbon atoms. Excess diamine can be employed to provide an excess of amine end groups over carboxy end groups in the polyamide. Mixtures of polyamides can also be used, as can block polyrners and copolymers.
Examples of polyamides include copolymers of polyhexamethylene adipamide (66 nylon), polyhloY~methylene azellamide (69 nylon), polyhexamethylene seb~c~mi-le (610 nylon), and polyhexamethylene dodecanoamide (612 nylon), the polyamide produced by ring opening of l~çt~mc, i.e., polycaprol~t~m, polylauric l~ct~m, poly-11-amino---ndec~noic acid, ~is (par~minocyclohexyl) methane dodec~no~mide. It is also possible to use in this invention polyamides prepared by the copolymerization of two of the above polymers or terpolymerization of the above polymers or their components, e.g., for example, an adipic, isophthalic acid hexamethylene diamine copolymer.
Specifically, modified PA6.6 (particularly a 6.6-6 copolyrner), PA6, PA6.10, PA6.12, PA11, PA12, PA12.12, PA6/6.6 etc. may be used. Particularly preferred because of high physical properties is a 6.6 polymer.
There are no special restrictions as to molecular weight of the polyamides. Preferable are polyamides with a relative viscosity (RV) according to ASTM D789 of 20 to 70, preferably 30-60.
Phenol-aldehyde resins are linear condensation resins which are obtained by condensing phenols such as phenol, cresol, bis-phenol A, resorcinol, or phenol-cresol and higher alkyl substitutions of them, and ~ wo 94/2l723 215 ~ 3 3 G PCT/US94/02844 aldehydes such as formaldehyde or acetaldehyde. Such resins are sold commercially under the name novolac. A phenol-formaldehyde resin is ` preferred.
Other suitable phenol-c-~nt~inin~ compounds from which useful 5 resins can be produced are n- and isoalkyl phenols which contain up to 8 carbon atoms in the alkyl groups, naphthols, hydroxy diphenyls, hydroxy diphenyl ethers, hydroquinone, pyroc~tecllol, bis-(hydroxy-phenyl) alkanes or cyclo~lk~n~s having up to 20 carbon atoms, bis (hydroxyphenyl) sulphides (or sulfones) and hydroxy benzoic acids. The phenol-aldehyde resins can be prepared by known methods such as described in Houben-Weyl, Methoden der org~ni~chen Chemie, Vol. 14/2, 4th edition pages 274 et seq.
Cross-linked phenol-aldehyde resins can also be used if a resin of higher melt viscosity is desired. Cross-linking can be conducted in a known m~nner using an acid such as phosphoric acid or boric acid, PC13, or polyfunctional epoxides or isocyanates or a formaldehyde donor.
Preferred phenol-aldehyde resins have softening temperatures in the range of 40 to 200~, preferably above 100C; and molecular weights (Mw) in the range of 5,000-30,000, preferably 10,000-20,~00.
The flame retardant polyamide compositions can also contain conventional additives, fillers, and reinforcing agents such as lubricants, mold-release agents, stabilizers, dyes, pigments, color concentrates1 flow agents, glass and organic ~lbers, chalk, clay, quartz, and hydrated mineral fillers such as magnesium hydroxide. Fillers and reinror.;ing agents, when used, are used at concentrations of 10-50% based on the weight of the composition, preferably 10-30~o by weight.
The compositions of the invention are prepared by thoroughly mixing or dissolving melamine in the phenol-aldehyde resin, or the two can be added simultaneously or separately to the polyamide during a compounding step. Any of the other fillers and additives typically used in polyamide compo--n(ling, i.e., in an extruder/screw combination specifically intended for the compo--n(lin~ of powders and glass into thermoplastic resin, ~, can also be added at the same time. The resulting extrudate is cooled, pelletized and dried before molding the reslllting composition into shaped articles.
In the examples which follow, test bars at each condition described in the UL94 test were tested in order to give a percentage of the _ 2~58~36 wO 94121723 PCTIUS94/0284 total which fail by igniting the cotton. This percent failure can then through experience of the m~nnf~ctllring process and the variability in the test method itself be correlated with the ability to reliably make commercial flame retardant resins which con~i~tently pass the UL94 test at VO.
S Relative viscosity (RV) is measured according to ASTM D-789 in 90% formic acid. The Coll,parative Tracking Index (CTI) is conducted in accordance with IEC 112. Weight loss (%) is carried out by Isothermal Thermogravimetric Analysis (TGA) at 280C.
The invention can be further understood by the following examples in which parts and percentages are by weight unless indicated otherwise.
EX~MPLES
Ex~mple 1 Eighty (80) parts by weight of a polyamide 66/6 copolyrner (90%
by weight 66/10~o by weight 6 with RV 46-52) was tumble-blended with 10 parts by weight of melamine powder and 10 parts by weight of phenol-formaldehyde resin (novolac H~J 10424 having a softening point of 120C) together with minor amounts of process aids and lubricants typical for the compounding of poly~mides The resulting physical blend was then fed to a 28 mm twin screw extruder fitted with vacuum venting. The extruder barrel temperature settings were in the 260-270C range with a die temperature of 270C and screw speed of 300 rprn.
l'he resulting strand was cooled in water and pelletized. The reslllting granules were vacuum dried at 80C to a moisture content of less than 0.2~. The dried granules were then molded into the required test pieces using a standard thermoplastic molding m~ ine using a melt temperature of 270C and mold temperature of 60-70C.
The above procedure was repeated using (B) 15 parts of melamine and 5 parts of phenol-formaldehyde resin, and (C) 15 parts of melamine, 0 parts of phenol-formaldehyde resin, and 85 parts of copolymer.
The results are shown in Table 1.
FLAME RETARDANT POLYAMIDES
BACKCROUND OF THE rNVE~TlON
This invention relates to flame retardant polyamide compositions and more particularly to such compositions cont~ining a combination of melamine and phenol-aldehyde resins.
The use of melamine and melamine derivatives such as melamine cyanurate as flame retardant agents for polyamides has been known for many years (U.S. Patent 3,660,344 and U.S. Patent Re 30,402). In the case of polyamide 6.6, which is specifically used for its better thermal aging properties versus polyamide 6, the use of melamine as the flame retardant of choice has not been widely used commercially due to the fact that its volatility can lead to large amounts of white mold deposit and as previously noted (U.S. Patent 4,525,505) melamine can bleed from molded parts under various sim~ ted use conditions~ The alternative to melamine has been the use of melamine derivatives or its condensation products such as melamine cyanurate; but, although these have presented solutions to the melamine blooming issues, they have proved difficult to scale-up to typical commercial processes without some loss of fl~mm~ility control.
The volatility rate of melamine from polyamides containing it is comparable to melamine itself because of the incompatibility of melamine with poly~mides It has now been found that phenol-aldehyde resins, such as phenol-formaldehyde resins sold under the name novolac, reduce and in some cases elimin~te mold deposit and humid blooming of the melamine during compounding and molding of the polyamide compositions.
Polyamide compositions cont~ining a combination of melamine and a phenol-aldehyde resin according to the invention have the advantages of having a flame resistant rating of VO under E~94 and retaining their physical and electrical properties.
According to the present invention, provided is a flame retardant polyamide composition which comprises:
(a) 45-95% by weight of a polyamide, preferably 65-95% by weight, and most preferably 75-90% by weight;
(b) 2-30% by weight of mel~mine, preferably 2-15~ by weight, and most preferably 5-15% by weight; and ~15~36 (c) 2-30~o by weight of a phenol-aldehyde resin, preferably 2-15~ by weight, and most preferably 5-15% by weight; and optionally (d) 0-50% by weight, preferably 0-30~o by weight, of at least one of a reinforcing agent or filler. ?
When a reinforcing agent and/or filler are used, they are preferably used at a concentration of 10-30~o by weight.
Polyamides useful in the compositions of this invention are well known in the art and embrace those semi-crystalline and amorphous polymers having a molecular weight of at least 5000 and commonly referred to as nylons. Suitable polyamides include those described in U.S. Patent Nos. 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 3,312,966, 2,512,606, and 3,393,210. The polyamide can be produced by condensation of equimolar amounts of a saturated dicarboxylic acid cont~ininE from 4 to 12 carbon atoms with a diamine, in which the r1i~mine contains from 4 to 14 carbon atoms. Excess diamine can be employed to provide an excess of amine end groups over carboxy end groups in the polyamide. Mixtures of polyamides can also be used, as can block polyrners and copolymers.
Examples of polyamides include copolymers of polyhexamethylene adipamide (66 nylon), polyhloY~methylene azellamide (69 nylon), polyhexamethylene seb~c~mi-le (610 nylon), and polyhexamethylene dodecanoamide (612 nylon), the polyamide produced by ring opening of l~çt~mc, i.e., polycaprol~t~m, polylauric l~ct~m, poly-11-amino---ndec~noic acid, ~is (par~minocyclohexyl) methane dodec~no~mide. It is also possible to use in this invention polyamides prepared by the copolymerization of two of the above polymers or terpolymerization of the above polymers or their components, e.g., for example, an adipic, isophthalic acid hexamethylene diamine copolymer.
Specifically, modified PA6.6 (particularly a 6.6-6 copolyrner), PA6, PA6.10, PA6.12, PA11, PA12, PA12.12, PA6/6.6 etc. may be used. Particularly preferred because of high physical properties is a 6.6 polymer.
There are no special restrictions as to molecular weight of the polyamides. Preferable are polyamides with a relative viscosity (RV) according to ASTM D789 of 20 to 70, preferably 30-60.
Phenol-aldehyde resins are linear condensation resins which are obtained by condensing phenols such as phenol, cresol, bis-phenol A, resorcinol, or phenol-cresol and higher alkyl substitutions of them, and ~ wo 94/2l723 215 ~ 3 3 G PCT/US94/02844 aldehydes such as formaldehyde or acetaldehyde. Such resins are sold commercially under the name novolac. A phenol-formaldehyde resin is ` preferred.
Other suitable phenol-c-~nt~inin~ compounds from which useful 5 resins can be produced are n- and isoalkyl phenols which contain up to 8 carbon atoms in the alkyl groups, naphthols, hydroxy diphenyls, hydroxy diphenyl ethers, hydroquinone, pyroc~tecllol, bis-(hydroxy-phenyl) alkanes or cyclo~lk~n~s having up to 20 carbon atoms, bis (hydroxyphenyl) sulphides (or sulfones) and hydroxy benzoic acids. The phenol-aldehyde resins can be prepared by known methods such as described in Houben-Weyl, Methoden der org~ni~chen Chemie, Vol. 14/2, 4th edition pages 274 et seq.
Cross-linked phenol-aldehyde resins can also be used if a resin of higher melt viscosity is desired. Cross-linking can be conducted in a known m~nner using an acid such as phosphoric acid or boric acid, PC13, or polyfunctional epoxides or isocyanates or a formaldehyde donor.
Preferred phenol-aldehyde resins have softening temperatures in the range of 40 to 200~, preferably above 100C; and molecular weights (Mw) in the range of 5,000-30,000, preferably 10,000-20,~00.
The flame retardant polyamide compositions can also contain conventional additives, fillers, and reinforcing agents such as lubricants, mold-release agents, stabilizers, dyes, pigments, color concentrates1 flow agents, glass and organic ~lbers, chalk, clay, quartz, and hydrated mineral fillers such as magnesium hydroxide. Fillers and reinror.;ing agents, when used, are used at concentrations of 10-50% based on the weight of the composition, preferably 10-30~o by weight.
The compositions of the invention are prepared by thoroughly mixing or dissolving melamine in the phenol-aldehyde resin, or the two can be added simultaneously or separately to the polyamide during a compounding step. Any of the other fillers and additives typically used in polyamide compo--n(ling, i.e., in an extruder/screw combination specifically intended for the compo--n(lin~ of powders and glass into thermoplastic resin, ~, can also be added at the same time. The resulting extrudate is cooled, pelletized and dried before molding the reslllting composition into shaped articles.
In the examples which follow, test bars at each condition described in the UL94 test were tested in order to give a percentage of the _ 2~58~36 wO 94121723 PCTIUS94/0284 total which fail by igniting the cotton. This percent failure can then through experience of the m~nnf~ctllring process and the variability in the test method itself be correlated with the ability to reliably make commercial flame retardant resins which con~i~tently pass the UL94 test at VO.
S Relative viscosity (RV) is measured according to ASTM D-789 in 90% formic acid. The Coll,parative Tracking Index (CTI) is conducted in accordance with IEC 112. Weight loss (%) is carried out by Isothermal Thermogravimetric Analysis (TGA) at 280C.
The invention can be further understood by the following examples in which parts and percentages are by weight unless indicated otherwise.
EX~MPLES
Ex~mple 1 Eighty (80) parts by weight of a polyamide 66/6 copolyrner (90%
by weight 66/10~o by weight 6 with RV 46-52) was tumble-blended with 10 parts by weight of melamine powder and 10 parts by weight of phenol-formaldehyde resin (novolac H~J 10424 having a softening point of 120C) together with minor amounts of process aids and lubricants typical for the compounding of poly~mides The resulting physical blend was then fed to a 28 mm twin screw extruder fitted with vacuum venting. The extruder barrel temperature settings were in the 260-270C range with a die temperature of 270C and screw speed of 300 rprn.
l'he resulting strand was cooled in water and pelletized. The reslllting granules were vacuum dried at 80C to a moisture content of less than 0.2~. The dried granules were then molded into the required test pieces using a standard thermoplastic molding m~ ine using a melt temperature of 270C and mold temperature of 60-70C.
The above procedure was repeated using (B) 15 parts of melamine and 5 parts of phenol-formaldehyde resin, and (C) 15 parts of melamine, 0 parts of phenol-formaldehyde resin, and 85 parts of copolymer.
The results are shown in Table 1.
3 215 ~ 3 3 ~ PCT/US94/02844 Table 1 A B C
Polyamide 66/6 80 80 85 Copolymer (90/10) Melamine 10 15 15 NovolacHRJ 10424 10 5 0 UL94Fl~mm~bili~at 1.6 mm V-O V-O V-O
~ Wt Loss in 10 min at 280C 2.5 3.5 7 Blooming (Visual) After S Days at 70C/100~ RH None None Yes CTI (Volts) >600 >600 ~600
Polyamide 66/6 80 80 85 Copolymer (90/10) Melamine 10 15 15 NovolacHRJ 10424 10 5 0 UL94Fl~mm~bili~at 1.6 mm V-O V-O V-O
~ Wt Loss in 10 min at 280C 2.5 3.5 7 Blooming (Visual) After S Days at 70C/100~ RH None None Yes CTI (Volts) >600 >600 ~600
Claims (6)
1. A flame retardant polyamide composition which comprises:
(a) 45-95% by weight of a polyamide;
(b) 2-30% by weight of melamine;
(c) 2-30% by weight of a phenol-aldehyde resin;
and optionally (d) 0-50% by weight of at least one of a reinforcing agent or filler.
(a) 45-95% by weight of a polyamide;
(b) 2-30% by weight of melamine;
(c) 2-30% by weight of a phenol-aldehyde resin;
and optionally (d) 0-50% by weight of at least one of a reinforcing agent or filler.
2. A composition according to Claim 1 comprising (a) 65-95% by weight of a polyamide; (b) 2-15% by weight of melamine, and (c) 2-15% by weight of a phenol-aldehyde resin; and optionally (d) 0-30% by weight of at least one of a reinforcing agent or a filler.
3. A composition according to Claim 1 or Claim 2 wherein the polyamide is polyamide-6, polyamide-6.6, or a copolymer of polyamide-6 and polyamide-6.6.
4. A composition according to Claims 1-3 wherein the phenol-aldehyde resin is a phenol-formaldehyde resin.
5. A composition according to any of Claims 1-4 containing 10-30% by weight of at least one of a reinforcing agent or filler selected from glass fibers and mineral fillers.
6. A composition of any of Claims 1-5 in the form of a shaped article.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934308534 DE4308534A1 (en) | 1993-03-17 | 1993-03-17 | Flame retardant polyamides |
| DEP4308534.2 | 1993-03-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2158336A1 true CA2158336A1 (en) | 1994-09-29 |
Family
ID=6483061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2158336 Abandoned CA2158336A1 (en) | 1993-03-17 | 1994-03-16 | Flame retardant polyamides |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0689565A1 (en) |
| JP (1) | JP3406603B2 (en) |
| CA (1) | CA2158336A1 (en) |
| DE (1) | DE4308534A1 (en) |
| WO (1) | WO1994021723A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2794467B1 (en) * | 1999-06-04 | 2004-08-20 | Rhodia Eng Plastics Srl | FLAME RETARDANT POLYAMIDE COMPOSITION |
| FR2908418B1 (en) * | 2006-11-10 | 2012-08-17 | Rhodia Recherches & Tech | FLAME RETARDANT POLYAMIDE COMPOSITION. |
| FR2935144B1 (en) * | 2008-08-25 | 2011-12-16 | Rhodia Operations | USE OF A NOVOLAQUE RESIN FOR INCREASING THE ACID RESISTANCE OF A POLYAMIDE COMPOSITION |
| JP5504803B2 (en) * | 2009-09-30 | 2014-05-28 | 住友ベークライト株式会社 | Phenolic resin molding material |
| CN102337022A (en) * | 2011-05-31 | 2012-02-01 | 深圳市科聚新材料有限公司 | Nylon material special for breakers and preparation method thereof |
| US20190322805A1 (en) * | 2018-04-18 | 2019-10-24 | Invista North America S.A R.L. | Flame-retardant polyamide composition |
| CN109467925B (en) * | 2018-11-29 | 2021-03-23 | 上海金发科技发展有限公司 | Moisture-heat aging precipitation-resistant halogen-free flame-retardant nylon composite material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH515954A (en) * | 1968-10-17 | 1971-11-30 | Bayer Ag | Self-extinguishing polyamide molding compound |
| US3793289A (en) * | 1971-10-13 | 1974-02-19 | Allied Chem | Flame retardant nylon compositions |
| JPS5010408B2 (en) * | 1971-11-06 | 1975-04-21 | ||
| DE2800467A1 (en) * | 1978-01-05 | 1979-07-12 | Bayer Ag | FLAME RESISTANT POLYAMIDE MOLDING COMPOUNDS |
| DE2810549A1 (en) * | 1978-03-10 | 1979-09-13 | Bayer Ag | FLAME RESISTANT POLYAMIDE MOLDING COMPOUNDS |
| DE4141861A1 (en) * | 1991-12-18 | 1993-06-24 | Du Pont Int | FLAME-RESISTANT POLYAMID |
-
1993
- 1993-03-17 DE DE19934308534 patent/DE4308534A1/en not_active Withdrawn
-
1994
- 1994-03-16 WO PCT/US1994/002844 patent/WO1994021723A1/en not_active Application Discontinuation
- 1994-03-16 JP JP52121394A patent/JP3406603B2/en not_active Expired - Fee Related
- 1994-03-16 EP EP94911619A patent/EP0689565A1/en not_active Withdrawn
- 1994-03-16 CA CA 2158336 patent/CA2158336A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0689565A4 (en) | 1995-09-25 |
| JP3406603B2 (en) | 2003-05-12 |
| WO1994021723A1 (en) | 1994-09-29 |
| EP0689565A1 (en) | 1996-01-03 |
| DE4308534A1 (en) | 1994-09-22 |
| JPH08507826A (en) | 1996-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2902444B1 (en) | Polyamide moulding compounds with flame retardant properties and very good long-term heat ageing resistance | |
| US6500881B1 (en) | Flame-proofed polyamide composition | |
| US11104798B2 (en) | Thermoplastic polymer composition having improved mechanical properties | |
| US11492489B2 (en) | High heat resistance polyamide molding compound | |
| EP1572797B1 (en) | Flame retardant polyamide compound | |
| JP5166428B2 (en) | Flame retardant polyamide composition | |
| CN110903644A (en) | Bio-based PA56T and PA56 composite material and preparation method thereof | |
| CA2158336A1 (en) | Flame retardant polyamides | |
| CA3129447C (en) | Hydrolysis resistant polyamides | |
| CN111117233B (en) | Polyamide 56 composition resistant to corrosion of automobile coolant and preparation method and application thereof | |
| CN112745675A (en) | Halogen-free flame-retardant polyamide composite material and preparation method and application thereof | |
| EP3172273B1 (en) | Heat stabilized polyamide composition | |
| EP3945110A1 (en) | Flame retardant stabilizer combinations for flame-resistant polymers having improved resistance to hydrolysis and their use | |
| US5618864A (en) | Flame retardant polyamides | |
| EP0929600B1 (en) | Color stable flame retarded polyamide resin | |
| CN112708262B (en) | Polyamide composition and preparation method and application thereof | |
| DE60005006T3 (en) | FLAME-REDUCING POLYAMIDE COMPOSITION | |
| US5476887A (en) | Flame retardant polyamides | |
| CN116462963B (en) | Halogen-free flame-retardant reinforced nylon composition and preparation method and application thereof | |
| JP2001106900A (en) | Polyamide resin composition | |
| WO2023025741A1 (en) | Flame-proof, partially aromatic polyamides | |
| CH718923A2 (en) | Flame retardant, partially aromatic polyamides. | |
| CN114456595A (en) | Low-mold-scale polyamide composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |