CA2099479C - Flame-retardant polyamide moulding compositions - Google Patents
Flame-retardant polyamide moulding compositions Download PDFInfo
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- CA2099479C CA2099479C CA002099479A CA2099479A CA2099479C CA 2099479 C CA2099479 C CA 2099479C CA 002099479 A CA002099479 A CA 002099479A CA 2099479 A CA2099479 A CA 2099479A CA 2099479 C CA2099479 C CA 2099479C
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- polyamide
- moulding composition
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to flame-retardant polyamide compositions based on magnesium hydroxide with very good mechanical and electrical properties and high surface quality.
Description
~l c~
Flame- retardant polyamide mouldincr eom~ositions The invention relates to flame-retardant polyamide compositions based on magnesium hydroxide with very good mechanical and electrical properties and high surface quality.
Polyamides are engineerings thermoplasticSwith the characteristic features - good processability - very good mechanical properties - very good electrical properties - high deflection temperature - good chemical resistance - very high surface quality.
If polyamides of proven value are reinforced with glass fibres, glass spheres, mineral fillers or mixtures of these, their properties may be appreciably enhanced.
Elastomeric modification improves the impact strength of the reinforced polyamides. Novel products tailor-made for specific fields of application axe constantly being developed as a result of the many possible permutations.
However, the utilisation of mineral fillers and/or glass fibres is detrimental to surface quality.
Polyamides have long proved valuable in the electrical sector. The polyamides used in this field of application are mainly flame-retardant typs.
he A 29 202-foreign countries ~~~)~~~~~ , The following flame-retardant additives are well known and are used in polyamides since long time.
R~d 8hos~hoxus (eg DE-A-3 713 746 (= US-4 877 823) and EP-A 299 444 (= US-5 081 222)) is a flame-retardant agent normally supplied only in glass fibre-reinforced PA 66 and 6/6T. Such compounds are supplied only in dark colours due to the reddish brown colour inherent in the phosphorus, and its pigment-like character. They also have a tendency to form phosphine and phosphates under the influence of humidity and heat (as a result of a disproportionation reaction of the phosphorus). Phosphine causes toxicology problems and also corrodes the copper-containing contacts in electrical equipment. Phosphates form conductive deposits between the electrical contacts. Suitable stabilisers can retard the disproportionation reaction of the phosphorus but not suppress it completely.
~) Oryamic hslogen c~~ounds Brominated diphenyls or diphenylethers combined with antimony trioxide have long been utilised. Tncreasingly, use is made of the following halogen compounds:
- chlorinated cycloaliphatic hydrocarbons (Dechlorane~ plus, ex Occidental Chemical Co) - brominated styrene oligomers (DE-A-2703419) - polystyrenes brominated in the nucleus (PYRO-CHEK~
68, ex FERRO Chemicals) Zinc salts or iron oxides are today utilised as synergist.
The majority of halogen-based flame-retardant agents themselves begin to undergo decomposition at the Le A 29 202 ~w ~j (~ ~~ !~
Flame- retardant polyamide mouldincr eom~ositions The invention relates to flame-retardant polyamide compositions based on magnesium hydroxide with very good mechanical and electrical properties and high surface quality.
Polyamides are engineerings thermoplasticSwith the characteristic features - good processability - very good mechanical properties - very good electrical properties - high deflection temperature - good chemical resistance - very high surface quality.
If polyamides of proven value are reinforced with glass fibres, glass spheres, mineral fillers or mixtures of these, their properties may be appreciably enhanced.
Elastomeric modification improves the impact strength of the reinforced polyamides. Novel products tailor-made for specific fields of application axe constantly being developed as a result of the many possible permutations.
However, the utilisation of mineral fillers and/or glass fibres is detrimental to surface quality.
Polyamides have long proved valuable in the electrical sector. The polyamides used in this field of application are mainly flame-retardant typs.
he A 29 202-foreign countries ~~~)~~~~~ , The following flame-retardant additives are well known and are used in polyamides since long time.
R~d 8hos~hoxus (eg DE-A-3 713 746 (= US-4 877 823) and EP-A 299 444 (= US-5 081 222)) is a flame-retardant agent normally supplied only in glass fibre-reinforced PA 66 and 6/6T. Such compounds are supplied only in dark colours due to the reddish brown colour inherent in the phosphorus, and its pigment-like character. They also have a tendency to form phosphine and phosphates under the influence of humidity and heat (as a result of a disproportionation reaction of the phosphorus). Phosphine causes toxicology problems and also corrodes the copper-containing contacts in electrical equipment. Phosphates form conductive deposits between the electrical contacts. Suitable stabilisers can retard the disproportionation reaction of the phosphorus but not suppress it completely.
~) Oryamic hslogen c~~ounds Brominated diphenyls or diphenylethers combined with antimony trioxide have long been utilised. Tncreasingly, use is made of the following halogen compounds:
- chlorinated cycloaliphatic hydrocarbons (Dechlorane~ plus, ex Occidental Chemical Co) - brominated styrene oligomers (DE-A-2703419) - polystyrenes brominated in the nucleus (PYRO-CHEK~
68, ex FERRO Chemicals) Zinc salts or iron oxides are today utilised as synergist.
The majority of halogen-based flame-retardant agents themselves begin to undergo decomposition at the Le A 29 202 ~w ~j (~ ~~ !~
temperatures of polyamides. Corrosive gases form, resulting in destruction of the electrical contacts. The electrical properties of polyamides are, moreover, impaired by the ion-forming dissociation products.
These disadvantages are an accepted fact when preparing light-coloured components.
3) NitroQga coaaoounds Melamine salts have proved to be of value as flame-retardant agents only where unreinforced polyamides are involved. Such products are inherently light-coloured and are possessed of good electrical properties. The relatively low decomposition temperature of melamine salts is a disadvantage.
These disadvantages are an accepted fact when preparing light-coloured components.
3) NitroQga coaaoounds Melamine salts have proved to be of value as flame-retardant agents only where unreinforced polyamides are involved. Such products are inherently light-coloured and are possessed of good electrical properties. The relatively low decomposition temperature of melamine salts is a disadvantage.
4) Ma~nesiuxn by oxi~d~
Magnesium hydroxide is a known flame-retardant agent for use with polyolefines and elastomers. Compared with aluminium hydroxide, used hitherto, it has the advantage of a higher water dissociation temperature (> 340° C). The literature contains references describing the utilisation of magnesium hydroxide in polyamides. However, a quantity in excess of 55~ is required to achieve a flame-retardancy rating of V 0 using the Underwrites Laboratories Test Standard UL 94, at a thickness of 1.6 mm. Processing such products presents due to the high fillers content lot of problems. Impact strength, especially in the case of PA 66 are at low level. Beside that very poor surface quality are obtained.
Le A 29 202 In EP-A-0 335 165 (= US-4 963 610) from 0.1 to 20 wt-% of a functionalised olefine homopolymer or copolymer and from 3 to 30 wt-% of a reinforcing fibre are added to polyamide to produce flame-retardant compounds having from 40 to 70 wt-% of certain magnesium hydroxide species (specific surface area less than l8 m2/g). According to this publication, at a thickness of l.6 mm, a rating of V 0 in accordance with UL 94 is not achieved with magnesium hydroxide of any other type and not having olefineic additives. As a result of coupling of certain polyolefines with polyamide, and the high content levels; such compounds are very difficult to process.
The invention provides polyamide moulding compositions which are free of phosphorus (red) and halogen, but which are readily workable, and moulded components. therefrom, having, at a thickness of 1.6 mm, the classification V 0 in accordance with UL 94, and which additionally exhibit good mechanical properties and good surfaces.
It has now been found that the properties indicated are obtained by combining:
from 5 to 30 wt-% of a thermoplastic polyamide, from 10 to 30 wt-% of a thermoplastic partly aromatic copolyamide, from 0 to 25 wt-% reinforcements, from 40 to 60 wt-~ magnesium hydroxide, 5 from 0 to 2.0 wt-~ additives, such as lubricants, stabilisers and nucleating agents.
The invention provides flame-resistant polyamide moulding compositions of A) from 5 to 30 wt-~, and preferably from 10 to 25 wt-~, of a thermoplastic, partially crystalline polyamide, B) from 10 to 30 wt-~, and preferably from 15 to 28 wt -~, of a thermoplastic, partially crystalline, partly aromatic copolyamide, C) from 40 to 60 wt-~ of magnesium hydroxide, D) from 0 to 25 wt-~, and preferably from 5 to 23 wt-~, of reinforcements, E) from 0 to 2 wt-~ workability additives, the use of the polyamide moulding compositions for the preparation of moulded bodies and moulded bodies froiri the moulding compositions according to the invention.
The compositions according to the invention are prepared on commercial single- or twin-screw extruders or kneaders.
The magnesium hydroxide is dosed into the granulate in the feed hopper and/or into the polyamide melt through a side screw. The reinforcements D) (eg glass fibres) are dispensed into the glass fibre orifice a short distance upstream of the extruder head, in accordance with prior art. The temperature of the composition is matched to the polyamides used and is between 220 and 340° C.
Partly crystalline polyamides (PA), in particular PA 6, PA
66, PA 46, PA 610, PA 6/6T or partially crystalline copolyamides or mixtures based on these components, are suitable as thermoplastic polyamide A) of the moulding compositions according to the invention.
Compounds which are suitable as partly aromatic copolyamide B) of the moulding compositions according to the invention are preferably copolyamides of isophthalic acid hexamethylenediamine and/or terephthalic acid hexamethylenediamine and caprolactam.
Commercial glass fibres and/or carbon fibres and/or mineral fibres, optionally with surface treatment for polyamides, and preferably glass fibres, are used as the reinforcements D) for the moulding compositions according to the invention.
Commercial magnesium hydroxide, with or without surface treatment, is used as magnesium hydroxide C) according to the present invention. A marked improvement in the mechanical properties results from surface-treating the magnesium hydroxide with aminosilanes. Finely-particulate (diameter: 0.4-l0u) Mg hydroxides may preferably be used according to the present invention.
The workability additives E) comprise commercial lubricants, heat stabilisers and/or nucleating agents.
Le A 29 202 ~v~t~-~7~J
After premixing, the ingredients were extruded at a temperature of 290° C in a twin--screw continuous kneader and compounder, and then granulated. The granulate obtained was dried at 70° C in a vacuum drying cabinet for 4 h. and then injection-moulded in an Arburg injection moulding machine at a material temperature of 290° C to form test pieces.
The mechanical and electrical properties, fire retardancy in accordance with UL 94 and surface quality were determined (cf. Tables 1 and 2).
Le A 29 202 N~~q~,~ ~'~
Table 1 Test 1 2 3 4 5 Compa- Compa-rative rative Polyamide 45.4 40.2 19.2 17.0 16.9 Copolyamide 0.0~ 0.0~ 26.2 23.2 22.9 of 85 wt-$
polyamide and 15 wt-~
polyamide 6,I
Mg(OA)2 54.5 51.7 54.5 51.7 45.1 Glass fibres 0.0~ 8.0~ 0.0~ 8.0~ 15.0 Amide wax 0.1~ 0.1~ 0.1~ 0.1~ 0.1~
Izod an[kJ/m2] 23 25 25 25 26 Surface + -- +++ ++ ++
quality Fireproofing rating to Testing Standard at 3.2 mm V 0 V O V O V O V O
1.6 mm V 2 V 0 V 0 V 0 V 0 0.8 mm V 2 V 2 V 2 V 2 V 0 Resistance 4o to glowing wire ( C) 960 960 960 960 960 Tracking > 600 > 600 > 600 > 600 > 600 resistance (to IEC 112 or VDO 303 T1) Le A 29 202 l ~ ~ (! ;'~
'~
Test 6 7 8 9 10 Compa- Compa-rative rative Polyamide 45.4 40.2 19.2 17.0 16.9 Copolyamide 0.0~ 0.0~ 26.2 23.25 22.9 of 85 wt-~
polyamide 10and 15 wt-~
polyamide 6,I
Mg(OH)2 54.5 51.7 54.5 51.7 45.1 15Glass fibres 0.0~ 8.0~ 0.0~ 8.0~ 15.0 Amide wax 0.1~ 0.1~ 0.1~ 0.1~ 0.1~
Izod 20an[kJ/m2] 16 19 23 26 27 Surface -- -- +++ ++ ++
quality 25Fireproofing rating to Testing Standard at 3.2 mm V 0 V 0 V 0 V 0 V 0 1.6 mm V 2 V 0 V 0 V 0 V 0 0.8 mm V 2 V 2 V 2 V 2 V 0 Resistance to glowing wire ( C) 960 960 960 960 960 40Tracking > 600 > 600 > 600 > 600 > 600 resistance (to IEC 112 or VDO 303 T1) Le A 29 202 Surface quality was classified as follows:
-- unsatisfactory (discoloured, rough, etc.) - imperfect + satisfactory ++ good +++ excellent (smooth, uniform colour) If test pieces from prior art moulding compositions and those from the special mixtures according to the invention are compared (Examples 1 with 3, 2 with 4, 6 with 8 and 7 with 9), it will be noted that surface quality increases markedly in each case. Whereas resistance to a glowing wire and tracking resistance remain constant, the moulded pieces according to the invention are placed in the higher flame-retardant classification, V 0, rather than V 2, in -accordance with Test Standard UL 94, at a thickness of 1.6 mm.
Le A 29 202
Magnesium hydroxide is a known flame-retardant agent for use with polyolefines and elastomers. Compared with aluminium hydroxide, used hitherto, it has the advantage of a higher water dissociation temperature (> 340° C). The literature contains references describing the utilisation of magnesium hydroxide in polyamides. However, a quantity in excess of 55~ is required to achieve a flame-retardancy rating of V 0 using the Underwrites Laboratories Test Standard UL 94, at a thickness of 1.6 mm. Processing such products presents due to the high fillers content lot of problems. Impact strength, especially in the case of PA 66 are at low level. Beside that very poor surface quality are obtained.
Le A 29 202 In EP-A-0 335 165 (= US-4 963 610) from 0.1 to 20 wt-% of a functionalised olefine homopolymer or copolymer and from 3 to 30 wt-% of a reinforcing fibre are added to polyamide to produce flame-retardant compounds having from 40 to 70 wt-% of certain magnesium hydroxide species (specific surface area less than l8 m2/g). According to this publication, at a thickness of l.6 mm, a rating of V 0 in accordance with UL 94 is not achieved with magnesium hydroxide of any other type and not having olefineic additives. As a result of coupling of certain polyolefines with polyamide, and the high content levels; such compounds are very difficult to process.
The invention provides polyamide moulding compositions which are free of phosphorus (red) and halogen, but which are readily workable, and moulded components. therefrom, having, at a thickness of 1.6 mm, the classification V 0 in accordance with UL 94, and which additionally exhibit good mechanical properties and good surfaces.
It has now been found that the properties indicated are obtained by combining:
from 5 to 30 wt-% of a thermoplastic polyamide, from 10 to 30 wt-% of a thermoplastic partly aromatic copolyamide, from 0 to 25 wt-% reinforcements, from 40 to 60 wt-~ magnesium hydroxide, 5 from 0 to 2.0 wt-~ additives, such as lubricants, stabilisers and nucleating agents.
The invention provides flame-resistant polyamide moulding compositions of A) from 5 to 30 wt-~, and preferably from 10 to 25 wt-~, of a thermoplastic, partially crystalline polyamide, B) from 10 to 30 wt-~, and preferably from 15 to 28 wt -~, of a thermoplastic, partially crystalline, partly aromatic copolyamide, C) from 40 to 60 wt-~ of magnesium hydroxide, D) from 0 to 25 wt-~, and preferably from 5 to 23 wt-~, of reinforcements, E) from 0 to 2 wt-~ workability additives, the use of the polyamide moulding compositions for the preparation of moulded bodies and moulded bodies froiri the moulding compositions according to the invention.
The compositions according to the invention are prepared on commercial single- or twin-screw extruders or kneaders.
The magnesium hydroxide is dosed into the granulate in the feed hopper and/or into the polyamide melt through a side screw. The reinforcements D) (eg glass fibres) are dispensed into the glass fibre orifice a short distance upstream of the extruder head, in accordance with prior art. The temperature of the composition is matched to the polyamides used and is between 220 and 340° C.
Partly crystalline polyamides (PA), in particular PA 6, PA
66, PA 46, PA 610, PA 6/6T or partially crystalline copolyamides or mixtures based on these components, are suitable as thermoplastic polyamide A) of the moulding compositions according to the invention.
Compounds which are suitable as partly aromatic copolyamide B) of the moulding compositions according to the invention are preferably copolyamides of isophthalic acid hexamethylenediamine and/or terephthalic acid hexamethylenediamine and caprolactam.
Commercial glass fibres and/or carbon fibres and/or mineral fibres, optionally with surface treatment for polyamides, and preferably glass fibres, are used as the reinforcements D) for the moulding compositions according to the invention.
Commercial magnesium hydroxide, with or without surface treatment, is used as magnesium hydroxide C) according to the present invention. A marked improvement in the mechanical properties results from surface-treating the magnesium hydroxide with aminosilanes. Finely-particulate (diameter: 0.4-l0u) Mg hydroxides may preferably be used according to the present invention.
The workability additives E) comprise commercial lubricants, heat stabilisers and/or nucleating agents.
Le A 29 202 ~v~t~-~7~J
After premixing, the ingredients were extruded at a temperature of 290° C in a twin--screw continuous kneader and compounder, and then granulated. The granulate obtained was dried at 70° C in a vacuum drying cabinet for 4 h. and then injection-moulded in an Arburg injection moulding machine at a material temperature of 290° C to form test pieces.
The mechanical and electrical properties, fire retardancy in accordance with UL 94 and surface quality were determined (cf. Tables 1 and 2).
Le A 29 202 N~~q~,~ ~'~
Table 1 Test 1 2 3 4 5 Compa- Compa-rative rative Polyamide 45.4 40.2 19.2 17.0 16.9 Copolyamide 0.0~ 0.0~ 26.2 23.2 22.9 of 85 wt-$
polyamide and 15 wt-~
polyamide 6,I
Mg(OA)2 54.5 51.7 54.5 51.7 45.1 Glass fibres 0.0~ 8.0~ 0.0~ 8.0~ 15.0 Amide wax 0.1~ 0.1~ 0.1~ 0.1~ 0.1~
Izod an[kJ/m2] 23 25 25 25 26 Surface + -- +++ ++ ++
quality Fireproofing rating to Testing Standard at 3.2 mm V 0 V O V O V O V O
1.6 mm V 2 V 0 V 0 V 0 V 0 0.8 mm V 2 V 2 V 2 V 2 V 0 Resistance 4o to glowing wire ( C) 960 960 960 960 960 Tracking > 600 > 600 > 600 > 600 > 600 resistance (to IEC 112 or VDO 303 T1) Le A 29 202 l ~ ~ (! ;'~
'~
Test 6 7 8 9 10 Compa- Compa-rative rative Polyamide 45.4 40.2 19.2 17.0 16.9 Copolyamide 0.0~ 0.0~ 26.2 23.25 22.9 of 85 wt-~
polyamide 10and 15 wt-~
polyamide 6,I
Mg(OH)2 54.5 51.7 54.5 51.7 45.1 15Glass fibres 0.0~ 8.0~ 0.0~ 8.0~ 15.0 Amide wax 0.1~ 0.1~ 0.1~ 0.1~ 0.1~
Izod 20an[kJ/m2] 16 19 23 26 27 Surface -- -- +++ ++ ++
quality 25Fireproofing rating to Testing Standard at 3.2 mm V 0 V 0 V 0 V 0 V 0 1.6 mm V 2 V 0 V 0 V 0 V 0 0.8 mm V 2 V 2 V 2 V 2 V 0 Resistance to glowing wire ( C) 960 960 960 960 960 40Tracking > 600 > 600 > 600 > 600 > 600 resistance (to IEC 112 or VDO 303 T1) Le A 29 202 Surface quality was classified as follows:
-- unsatisfactory (discoloured, rough, etc.) - imperfect + satisfactory ++ good +++ excellent (smooth, uniform colour) If test pieces from prior art moulding compositions and those from the special mixtures according to the invention are compared (Examples 1 with 3, 2 with 4, 6 with 8 and 7 with 9), it will be noted that surface quality increases markedly in each case. Whereas resistance to a glowing wire and tracking resistance remain constant, the moulded pieces according to the invention are placed in the higher flame-retardant classification, V 0, rather than V 2, in -accordance with Test Standard UL 94, at a thickness of 1.6 mm.
Le A 29 202
Claims (14)
1. Flame-retardant polyamide moulding compositions, comprising:
A) from 5 to 30 wt-% of thermoplastic, partially crystalline polyamide, B) from 10 to 30 wt-% of thermoplastic, partially crystalline, partly aromatic copolyamide, C) from 40 to 60 wt-% of magnesium hydroxide, D) from 0 to 25 wt-% of reinforcement, and E) from 0 to 2 wt-% of workability additives.
A) from 5 to 30 wt-% of thermoplastic, partially crystalline polyamide, B) from 10 to 30 wt-% of thermoplastic, partially crystalline, partly aromatic copolyamide, C) from 40 to 60 wt-% of magnesium hydroxide, D) from 0 to 25 wt-% of reinforcement, and E) from 0 to 2 wt-% of workability additives.
2. The moulding composition according to claim 1, comprising from 10 to 25 wt-% of polyamide A).
3. The moulding composition according to claim 1 or 2, comprising from 15 to 28 wt-% of copolyamide B).
4. The moulding composition according to claim 1, 2 or 3, comprising from 5 to 23 wt-% of reinforcements.
5. The moulding composition according to any one of claims 1 to 4, wherein the thermoplastic, partially crystalline polyamide A) comprises polyamide 6, polyamide 66, polyamide 46, polyamide 610, polyamide 6/6T, a partially crystalline copolyamide based on said polyamides, or a mixture based on said polyamides.
6. The moulding composition according to any one of claims 1 to 5, wherein the partly aromatic, partially crystalline copolyamide B) comprises isophthalic acid hexamethylenediamine and/or terephthalic acid hexamethylenediamine and caprolactam.
7. The moulding composition according to claim 6, wherein the partly aromatic copolyamide B) comprises caprolactam, isophthalic acid and hexamethylenediamine.
8. The moulding composition according to any one of claims 1 to 7, wherein glass fibres, carbon fibres, mineral fibres or mixtures thereof are used as the reinforcement D).
9. The moulding compositions according to claims 1 to 8, characterised in that glass fibres are used as the reinforcement.
10. The moulding composition according to any one of claims 1 to 9, wherein the magnesium hydroxide has a particle diameter of 0.4 to 10 µ.
11. The moulding composition according to claim 10, wherein the magnesium hydroxide is surface treated with an aminosilane.
12. The moulding composition according to any one of claims 1 to 11, wherein the workability additive E) is selected from the group consisting of a lubricant, a heat stabiliser, a nucleating agent and a mixture thereof.
13. Use of a moulding composition according to any one of claims 1 to 12, for the preparation of moulded parts.
14. A moulded part prepared from the moulding composition according to any one of claims 1 to 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4221925.6 | 1992-07-03 | ||
| DE4221925A DE4221925A1 (en) | 1992-07-03 | 1992-07-03 | Flame retardant polyamide molding compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2099479A1 CA2099479A1 (en) | 1994-01-04 |
| CA2099479C true CA2099479C (en) | 2004-08-03 |
Family
ID=6462438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002099479A Expired - Fee Related CA2099479C (en) | 1992-07-03 | 1993-06-30 | Flame-retardant polyamide moulding compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0576951B1 (en) |
| JP (1) | JP3355495B2 (en) |
| CA (1) | CA2099479C (en) |
| DE (2) | DE4221925A1 (en) |
| ES (1) | ES2115697T3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06240135A (en) * | 1993-01-07 | 1994-08-30 | Bayer Ag | Highly flame-retardant polyamide molding composition |
| GB2274109B (en) * | 1993-01-08 | 1996-07-03 | T & N Technology Ltd | Moulding compositions containing nylon |
| JP3523312B2 (en) * | 1993-12-28 | 2004-04-26 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Flame retardant polyamide resin composition |
| GB2288808A (en) * | 1994-04-19 | 1995-11-01 | T & N Technology Ltd | Moulding compositions containing a polyamide |
| AT405410B (en) * | 1997-05-21 | 1999-08-25 | Chemie Linz Gmbh | INTUMESCENT SEALING AND COVER PROFILES |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3810519C1 (en) * | 1988-03-28 | 1989-10-12 | Ems-Inventa Ag, Zuerich, Ch | |
| DE3917600A1 (en) * | 1989-05-31 | 1990-12-06 | Basf Ag | THERMOPLASTIC MOLDING PARTICLES AND PARTICULAR AMPOULE COPOLYAMIDES |
| DE3927321A1 (en) * | 1989-08-18 | 1991-02-21 | Bayer Ag | COPOLYAMIDES WITH INCREASED GLASS TRANSITION TEMPERATURE |
-
1992
- 1992-07-03 DE DE4221925A patent/DE4221925A1/en not_active Withdrawn
-
1993
- 1993-06-21 ES ES93109874T patent/ES2115697T3/en not_active Expired - Lifetime
- 1993-06-21 DE DE59308491T patent/DE59308491D1/en not_active Expired - Lifetime
- 1993-06-21 EP EP93109874A patent/EP0576951B1/en not_active Expired - Lifetime
- 1993-06-28 JP JP18192193A patent/JP3355495B2/en not_active Expired - Lifetime
- 1993-06-30 CA CA002099479A patent/CA2099479C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4221925A1 (en) | 1994-01-05 |
| DE59308491D1 (en) | 1998-06-10 |
| JP3355495B2 (en) | 2002-12-09 |
| CA2099479A1 (en) | 1994-01-04 |
| ES2115697T3 (en) | 1998-07-01 |
| EP0576951A1 (en) | 1994-01-05 |
| JPH0657134A (en) | 1994-03-01 |
| EP0576951B1 (en) | 1998-05-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |