JP3037573B2 - Flame-retardant polyamide and flame-retardant molding material and molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant molding material or a flame-retardant molding made of a thermoplastic polyamide.

[0002]

In the prior art, flame retardants for the production of flame-resistant polycondensation products are disclosed, for example, in U.S. Pat.
S) No. 3,418,267, German Patent Application Publication (DE-AS) 1,694,494, German Patent Application Publication (DE-AS) 1,931,387, and German Patent Publication (DE-OS) 2,544,219. The description of the book usually recommends a halogen compound in combination with antimony trioxide or its formulation.

[0003] Despite their good effects, halogen compounds which are suitable as flame retardants are associated with serious disadvantages in their use. They are described in detail in EP 0044 419 and German Patent (D).
E) No. 3,208,486. A particularly serious drawback is that in the case of the use of perbrominated aromatic compounds, such as decabromdiphenyl oxide, toxic compounds such as dioxins and furans are produced on loss of combustion, which are a serious harm to health. Bring.

It is known to use the elemental phosphorus in addition to halogen compounds to make thermoplastics, especially polyamides, flame-resistant. This processing method
It is described in German Patent Application Publication (DE-AS) 1 173 641 and U.S. Patent (US-PS) 3951908. In these cases, too, a series of disadvantages, such as the formation of phosphines, must be accepted during combustion. In addition, the color as well as the electrical properties are negatively affected. In this regard, the European patent (EP-B)
No. 0044419 reports.

[0005] Magnesium hydroxide and aluminum and nitrogen-containing compounds such as melamine, melamine cyanurate and cyanoguanidine are only limitedly suitable as flame retardants in polyamides. These are the UL of Underwriter Laboratories
To achieve a V0 rating according to the -94 specification, a large amount should be used. Due to this, the mechanical properties
Very varied.

[0006] Such flameproofing agents are disclosed, inter alia, in US Pat.
-PS) No. 4263203, U.S. Pat.
PS) 4001177, German Patent Publication (D)
E-OS) 2937379, German Patent Application Publication (DE-AS) 1694254, German Patent (DE-PS) 4127112 and German Patent Publication (DE-OS) 3909145. It is proposed in the book.

US Pat. No. 3,789,091
Specification and U.S. Patent (US-PS) 3849368
In this specification, cyclic phosphate esters are described as flame retardant additives for different homopolymers (including PA6.6), but the teachings of these patents teach: It does not solve the unique problems of VO-grade polyamides. Such compounds exhibit obvious migration disadvantages in partially crystalline polyamides.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a VO-Qualifikation flame-retardant polyamide and a flame-retardant molding material or molded article which can be produced therefrom. The molding materials or moldings should then have good mechanical and thermal properties and they should meet the V0-class according to UL-94, show no migration and usually Has the same electrical characteristics as those of the polyamides.

[0009]

This object is achieved by a V0-grade flame-retardant polyamide according to claim 1 and by a flame-retardant molding material or molding according to claims 14 and 15. The invention relates to the polyamides of the invention as well as the general formula I:

[0010]

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Wherein R and R ′ are independently of each other C
_A C ₁ -C ₄ -alkyl radical and X = 0 or 1].

[0012] Advantageous embodiments of the invention are covered by the claims.

This problem is solved in particular by non-migrated phosphonic compounds as flame retardant additives. The molding materials or moldings according to the invention are therefore particularly advantageous since they do not show any obstructive deposit formation.

Another advantage is the mechanical and electrical properties of the polyamide, each of which is a molded body, which are not actually changed by the flame retardant additive.

The molding materials or moldings according to the invention generally have an additive proportion of from 0.5 to 15% by weight, preferably from 4 to 8% by weight, based on the polyamide fraction, of which V0 −
It is also particularly advantageous that the composition be modified to be flame-retardant to such an extent that it achieves a grade. The V0-class is associated with test bars <0.8 mm thick.

[0016] Polyamide blends based on PA6 or PA12 have V0- values in the flammability test UL-94.
In general, about 5% by weight of the flame retardant additive is sufficient to achieve the value.

The thermoplastic polyamides and the flame-retardant molding materials or moldings are blends of the following: A) Partially crystalline polyamides 40-9
8% by weight B) Amorphous polyamide or copolyamide 2 to 60
weight%.

Preferred partially crystalline polyamides are the semicrystalline homopolyamides PA6, PA11, PA12, PA66, P
A69, PA610, PA612, PA1212, PA
46, but a monomer of the group of aliphatic diamines having 4 to 12 C atoms, cycloaliphatic diamines having 7 to 22 C atoms and aromatic diamines having 6 to 22 C atoms; With aliphatic dicarboxylic acids having from 4 to 12 C atoms, cycloaliphatic dicarboxylic acids having from 8 to 24 C atoms and aromatic dicarboxylic acids having from 8 to 20 C atoms Combinations are also advantageous.

As the amorphous polyamide type, polyamide PA12 / MACMI (PA12 / bis-methyl-p-aminocyclohexylmethane, isophthalic acid),
PA12 / MACMT (PA12 / bis-methyl-p-
Aminocyclohexylmethane, terephthalic acid), PA1
2 / MACMI / MACMT, PA6I, PA6I / 6
T, PA12 / MACM36 (Transparent amorphous copolyamide prepared from lactam 12, diamine 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and long-chain aliphatic dicarboxylic acid having 36 C atoms) , P
A NDT / INDT (PA trimethylhexamethylenediamine / isophthalic acid, trimethylhexamethylenediamine); PA6I / 6T / MACMI is preferred, but hexamethylenediamine and its derivatives, for example,
1,6-diamino-2,2,4-trimethylhexane and 1,6-diamino-2,4,4-trimethylhexane and bis- (p-aminocyclohexyl) methane and its derivatives and homologs, for example, 3, 3'-dimethyl-
Monomers of 4,4'-diamino-dicyclohexylmethane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine) and aliphatic or aromatic compounds having 4 to 36 or 8 to 20 carbon atoms From combinations with aromatic dicarboxylic acids (ISO-Criteria 1)
874) are also suitable.

The flame retardant additives belong to the group of the aliphatic polyol esters of alkylated phosphonic acids. Preferred additives are trimethylolpropanol esters of methylphosphonic acid according to formula I or the empirical formula C ₁₅ H ₃₁ O ₉
Methylphosphonic acid P ₃ - bis - [(5-ethyl-2-
Methyl-1,3,2-dioxaphospholinan-5-yl) -methyl] ester-P, P′-dioxide (this is Antiblase 1045 (Albright &
(Wilson, USA); CA
S: 42595-45-9):

[0021]

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[Where X = 0 or 1].

The thermoplastic molding materials or moldings according to the invention can be prepared with customary additives and processing aids, such as, for example, stabilizers, oxidation retarders, agents against thermal decomposition and decomposition by ultraviolet rays, lubricants, release agents, pigments. , Softeners, impact modifiers, fibrous and powdered fillers and reinforcing agents and conductivity additives, the proportion of which is generally less than 50% by weight, based on the total weight of the molding composition. It is.

As mentioned above, the molding materials or moldings according to the invention may be limited by the processing conditions according to the state of the art or may contain additives necessary for their use. Under similar conditions, molding materials or moldings which can be produced from formulations comprising the additives of the invention are PA, PET, PBT, PC,
Further polymers from the group of PVC, PVA, PU, PE, PP, PPS can be included, wherein these compounds further comprise impact modifiers, softeners, stabilizers, reinforcing agents, pigments , Dyes and fillers.

The molding material or molding contains the alkylphosphonic acid compound in a proportion of 0.5 to 15% by weight based on the polyamide content. The alkylphosphonic acid compound contains 4 to 10% by weight, preferably 5 to 10% by weight, based on the polyamide content.
Particular preference is given to molding compositions or moldings which are contained in a proportion by weight.

The moldings according to the invention can be produced by methods of the prior art, for example by injection molding, extrusion molding, coextrusion molding, suction molding or transfer molding.

The present invention relates to moldings of polyamides as flame-retardant additives of alkylphosphonic acid esters of aliphatic polyols and alkylated phosphonic acids, in particular trimethylolpropane ester of methylphosphonic acid. It also relates to the use for the production of molding materials. (Examples of the molded body include a fiber, a cable, a plug, and a plate.)

[0028]

【Example】

Examples 1-5 Preparation of polyamide blends A granulation mixture of Grilamid L20 type (component A) and a transparent TR55 type (component B) was prepared by WP
Melt in F-ZSK30 extruder. At that time, a flame retardant Antiblase 1045 (component C) was added.
It is metered into the melt using a heatable metering device.

The strands removed from the extruder are cooled in a water bath and ground in a conventional granulator. From this, DIN test bars for the measurement of the relevant properties are produced using an Arburg 320/210/750 injection molding machine.

Relative viscosity of component A 2.0 (0.5 g / 10 m-cresol)
0 (at 23 ° C.) with polyamide 12 (EMS-
GREMILA from CHEMIE AG (Zuerich)
mid) L20) or a relative viscosity of 4.0 (1 in H ₂ SO ₄ )
% (Polyamide 6) (EMS-CHEMIE A)
G (Zuerich) Grilon F40).

Component B Transparent CoPA12 / MACMI (EMS-CHEMI
EAG (Zuerich) Grillamide TR55) Component C Flame retardant antibrase 1045 from Albrigth & Wilson.

Examples 1 to 4 of the present invention show unchanged mechanical properties, similar electrical properties, V0-class according to UL-94, and actually show no migration as compared with the comparative examples.

[0033]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Manfred Hevel Roders Oberdorf, 34th Switzerland (56) References JP-A-5-311067 (JP, A) International Publication No. 92/13717 (WO, A1) (58 ) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 C08K 5/00-5/59 CA (STN) REGISTRY (STN)

Claims (15)

(57) [Claims] 1. A flame-retardant polyamideCompositionIn it
Has at least one general formula I as a flame retardant additive:Wherein R and R ′ are independently of each other C₁~ C₄-A
With a ruquil groupRAnd X = 0 or 1]
Contains phosphonic acid compoundsAnd polyamide (A) 40 to 98% by weight of semicrystalline polyamide (B) 2 to 60 weight of amorphous polyamide or copolyamide
% Characterized by flame-retardant poly
AmideComposition. 2. In formula I, R ′ is a C ₂ H ₅ — group,
The polyamide composition according to claim 1. 3. The method according to claim 1, wherein the alkylphosphonic acid compound is used in an amount of 0.5 to 0.5.
3. The polyamide composition according to claim 1, which is contained in the polyamide composition in a proportion of 15% by weight. Wherein a ratio of the alkyl phosphonic acid compound 4 to 10 wt% are contained in the polyamide composition, the polyamide composition according to claim 1 or 2. 5. The semi-crystalline polyamide monomer comprises 4 to 1
Aliphatic diamines having 2 C atoms, 7-22 C
Group of cyclic aliphatic diamines having atoms and aromatic diamines having 6 to 22 C atoms, aliphatic dicarboxylic acids having 4 to 36 C atoms, cyclic groups having 8 to 24 C atoms Claims: selected from the group consisting of aliphatic dicarboxylic acids and monomers of the group of aromatic dicarboxylic acids having 8 to 20 C atoms, or from the group of lactams or ω-aminocarboxylic acids. polyamide composition according to any one of 1 to 4. 6. The semicrystalline polyamide is PA6, PA11.
Or PA12, PA46, PA66, PA69, PA6
10, PA612, PA1212 and shall be the base polyamide composition according to claim 5. 7. The amorphous polyamide or copolyamide monomer is hexamethylenediamine and its derivatives, for example, 1,6-diamino-2,2 ′, 4-trimethylhexane and 1,6-diamino-2,4. , 4'-Trimethylhexane, bis- (p-aminocyclohexyl) methane and derivatives and homologs thereof, for example, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane,
A group of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), an aliphatic dicarboxylic acid having 4 to 36 C atoms and an aromatic dicarboxylic acid having 8 to 20 C atoms; The polyamide composition according to any one of claims 1 to 6, wherein the polyamide composition is selected from the combination of: 8. The amorphous polyamide is PA12 / MAC.
MI, PA12 / MACMT, PA12 / MACMI /
MACMT, PA6 I, PA6 I / 6T, PA12 / M
ACM36, PANDT / INDT and PA6 I / 6T
The polyamide composition of claim 7 , wherein the composition is selected from the group of / MACMI. 9. The flame retardant additive is an ester consisting of an aliphatic polyol and an alkylated phosphonic acid.
Polyamide according to any one of claims 1 to 8
Composition . 10. The method according to claim 1, wherein the flame retardant additive is a trimethylpropanol ester of methylphosphonic acid.
10. The polyamide composition according to any one of items up to 9 . 11. A polyamide composition comprising methyl-phosphonic acid-bis-[(5-ethyl-2-) as a flame retardant additive.
1,3,2- dioxaphosphorinane-5-yl) - methyl] ester -P, P'-dioxy containing de polyamide composition according to any one of claims 1 to 10 . 12. any one of claims 1 to 1 1
Flame-retardant molding materials or flame-retardant moldings can be produced from the polyamide composition according to. 13. any one of claims 1 to 1 1
A polyamide composition according to according to, polyamide (P
A), polyethylene terephthalate (PET), polybu
Tylene terephthalate (PBT), polycarbonate
(PC), polyvinyl Rukurorido (PVC), polyvinyl
Alcohol (PVA), polyurethane (PU), polye
Tylene (PE), polypropylene (PP), polyphenylene
Prepared from a blend with other polymers from the group of sulfides (PPS) , wherein the blend comprises a group of compounds from the group of impact modifiers, softeners, stabilizers, reinforcing agents, pigments, dyes and fillers. A flame-retardant molding material or a flame-retardant molded article which may be modified by an additive. The method according to claim 14 wherein at least one alkyl phosphonic acid compound, the polyamide composition component are contained in a proportion of 0.5 to 15 wt%, the molding material according to claim 1 2 or 1 3 or Molded body. 15. At least one alkylphosphonic acid compound is present in an amount of 4 to 10% by weight, based on the polyamide composition.
It is contained in a proportion of molding material or molded article according to claim 1 2 or 1 3.