TW201920416A - Flame-retardant polyamide compositions having high heat dimensional resistance and use thereof - Google Patents

Abstract

The invention relates to flame-retardant polyamide compositions comprising- polyamide having a melting point of not less than 290 DEG C as component A, - fillers and/or reinforcers as component B, - phosphinic salt of the formula (I) as component C, in which R1 and R2 are ethyl, M is Al, Fe, TiOp or Zn, m is 2 to 3, and p=(4-m)/2- compound selected from the group of the Al, Fe, TiOp and Zn salts of ethylbutylphosphinic acid, of dibutylphosphinic acid, of ethylhexylphosphinic acid, of butylhexylphosphinic acid and/or of dihexylphosphinic acid as component D, and - phosphonic salt of the formula (II) as component E, in which R3 is ethyl, Met is Al, Fe, TiOq or Zn, n is 2 to 3, and q=(4-n)/2, where the x-ray powder diffractogram of the compositions contains the following reflections: within the angle range 2[theta] from 9.099 DEG to 9.442 DEG, from 18.619 DEG to 18.984 DEG andfrom 26.268 DEG to 26.679 DEG and/or within the angle range 2[theta] from 5.112 DEG to 5.312 DEG, from 6.097 DEG to 6.297 DEG, from 10.082 DEG to 10.282 DEG, from 10.350 DEG to 10.550 DEG and from 12.308 DEG to 12.508 DEG and/or within the angle range 2[theta] from 9.117 DEG to 9.317 DEG and from 18.537 DEG to 18.737 DEG and/or within the angle range 2[theta] from 8.300 DEG to 8.500 DEG and from 14.765 DEG to 15.076 DEG. The polyamide compositions can be used for production of fibers, films and shaped bodies, especially for applications in the electricals and electronics sector.

Description

Flame retardant polyamidine composition with high heat resistance and use thereof

The present invention relates to a flame-retardant polyamide composition and a molded article produced therefrom, which are characterized by very good flame retardancy, high thermal resistance, and very good electrical properties.

Flammable plastics must generally be equipped with flame retardants in order to be able to meet the high flame retardancy requirements imposed by plastics processors and in some cases by legislators. Preferably-also for environmental reasons-use of halogen-free flame retardant systems which form only a small amount of smoke, if any.

Among these flame retardants, salts of phosphinic acid (phosphinate) have been found to be particularly effective for thermoplastic polymers (DE 2 252 258 A and DE 2 447 727 A).

In addition, it has been found that the synergistic combination of known phosphinates and specific nitrogen-containing compounds is more effective as a flame retardant in a full range of polymers than phosphinates alone (WO-2002 / 28953A1, and also DE 197 34 437 A1 and DE 197 37 727 A1).

US 7,420,007 B2 reveals that dialkylphosphinates containing a small amount of selected telomers as flame retardants are suitable for polymers that undergo only a relatively mild degree of flame retardant when added to the polymer matrix degradation.

Flame retardants must often be added in high doses to ensure that polymers according to international standards have sufficient flame retardancy. Due to the chemical reactivity necessary for high temperature flame retardancy, flame retardants, especially at higher doses, can impair the processing stability of plastics. This can lead to increasing polymer degradation, crosslinking reactions, degassing or discoloration.

WO 98/03515 A1 discloses high-temperature modified x-ray reflection of aluminum salts of phosphinic acid. The phosphinates are prepared at high temperatures.

WO 2014/135256 A1 discloses a polyamide molding compound having significantly improved thermal stability, reduced migration tendency, and good electrical and mechanical properties.

However, until now there has been a lack of a phosphinate-containing flame retardant polyamide composition that simultaneously achieves all required properties such as good electrical values, excellent thermal dimensional resistance, and effective flame retardancy.

Therefore, an object of the present invention is to provide a flame retardant polyamidoamine composition based on a phosphinate-containing flame retardant system, which simultaneously has all the above-mentioned properties and particularly has good electrical values (GWFI, CTI), excellent The thermal dimensional resistance (HDT-A) and high flame resistance are characterized by the shortest afterflame time (UL-94).

Therefore, the present invention provides a flame-retardant polyamidamine composition comprising:
-Polyamine having a melting point of not less than 290 ° C, preferably not less than 290 ° C, and most preferably not less than 300 ° C, as component A,
-Fillers and / or reinforcements, preferably glass fibers, as component B,
-A phosphinate of formula (I) as component C,

Where R ₁ and R ₂ are ethyl groups,
M is Al, Fe, TiO _p or Zn,
m is 2 to 3, preferably 2 or 3, and
p = (4-m) / 2,
-Selected from the group consisting of Al, Fe, TiO _p and Zn salts of ethylbutyl phosphinic acid, dibutyl phosphinic acid, ethylhexyl phosphinic acid, butylhexyl phosphinic acid and / or dihexyl phosphinic acid A group of compounds as component D, and
-A phosphonate of formula (II) as component E,

Where R ₃ is ethyl,
Met is Al, Fe, TiO _q or Zn,
n is 2 to 3, preferably 2 or 3, and
q = (4-n) / 2, where the x-ray powder diffraction pattern of the composition contains the following reflections:
In the angle range 2θ from 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 °, and / or in the angle range 2θ from 5.112 ° to 5.312 °, from 6.097 ° to 6.297 °, from 10.082 ° to 10.282 °, from 10.350 ° to 10.550 ° and from 12.308 ° to 12.508 °, and / or from the angle range 2θ from 9.117 ° to 9.317 ° and from 18.537 ° to 18.737 °, and / or from the angle range 2θ from 8.300 ° to 8.500 °.

The x-ray spectrum is recorded with an x-ray powder diffractometer (for example with Philips' X'Pert-MPD instrument). The sample was irradiated with Cu-K-α radiation, and the step time was 1 second.

The preferred polyester composition of the present invention has an X-ray powder diffraction pattern including the following reflections: in the angle range 2θ from 9.099 ° to 9.442 °, from 18.619 ° to 18.984 °, and from 26.268 ° to 26.679 °.

In the polyamidoamine composition of the present invention, the proportion of component A is usually 25% to 95% by weight, and preferably 25% to 75% by weight.

In the polyamidoamine composition of the present invention, the proportion of component B is usually 1% to 45% by weight, preferably 20% to 40% by weight.

In the polyamidoamine composition of the present invention, the proportion of component C is usually 1% to 35% by weight, preferably 5% to 20% by weight.

In the polyamidoamine composition of the present invention, the proportion of component D is usually 0.01% to 3% by weight, preferably 0.05% to 1.5% by weight.

In the polyamidoamine composition of the present invention, the proportion of component E is usually 0.001% by weight to 1% by weight, preferably 0.01% by weight to 0.6% by weight.

These percentages of the proportions of components A to E are based on the total amount of the polyamide composition.

Preference is given to flame-retardant polyamides, of which
-The proportion of component A is 25% to 95% by weight,
-The proportion of component B is from 1% to 45% by weight,
-The proportion of component C is from 1% to 35% by weight,
-The proportion of component D is 0.01% to 3% by weight, and
-The proportion of component E is 0.001% to 1% by weight,
These percentages are based on the total amount of the polyamide composition.

Particularly preferred is a flame-retardant polyamide composition, of which
-The proportion of component A is 25% to 75% by weight,
-The proportion of component B is 20% to 40% by weight,
-The proportion of component C is 5 to 20% by weight,
-The proportion of component D is from 0.05% to 1.5% by weight, and
-The proportion of component E is from 0.01% to 0.6% by weight.

The salt M ^{m +} of component C which is preferably used is a salt of Zn ²⁺ , Fe ³⁺ or especially Al ³⁺ .

The salts of component D which are preferably used are zinc salts, iron salts or especially aluminum salts.

The salt Met ^{n +} of component E which is preferably used is a salt of Zn ²⁺ , Fe ³⁺ or especially Al ³⁺ .

Very particular preference is given to M and Met based Al, m and n based 3, and the compound of component D is a flame-retardant polyamidoamine composition in the form of an aluminum salt.

In a preferred embodiment, the flame-retardant polyamidoamine composition further includes an inorganic phosphonate as another component F.

The use of inorganic phosphonates or phosphites (phosphite) of component F of the invention as flame retardants is known. For example, WO 2012/045414 A1 discloses a flame retardant combination that also contains, in addition to phosphinate, a salt of phosphorous acid (= phosphite).

Preferably, the inorganic phosphonate (component F) conforms to formula (IV) or (V)

Where Kat is a p-valent cation, especially an alkali metal or alkaline earth metal cation, ammonium cation, and / or Fe, Zn or especially Al cation, including the cations Al (OH) or Al (OH) ₂ , and p is 1, 2, 3 or 4.

Preferably, the inorganic phosphonate (component F) is aluminum hydrogen phosphite [Al (H ₂ PO ₃ ) ₃ ], secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], alkali Formula Aluminum Hydrophosphite [Al (OH) (H ₂ PO ₃ ) ₂ * 2aq], Aluminum Phosphite Tetrahydrate [Al ₂ (HPO ₃ ) ₃ * 4aq], Aluminum Phosphate, Al ₇ (HPO ₃ ) ₉ ( OH) ₆ (1,6-hexanediamine) _1.5 * 12H ₂ O, Al ₂ (HPO ₃ ) ³ * xAl ₂ O ₃ * nH ₂ O, where x = 2.27 to 1 and / or Al ₄ H ₆ P ₁₆ O ₁₈ .

The inorganic phosphonate (component F) preferably also contains aluminum phosphites of formula (VI), (VII) and / or (VIII),

Where q is 0 to 4,

Where M represents an alkali metal cation, z is 0.01 to 1.5, y is 2.63 to 3.5, and v is 0 to 2 and w is 0 to 4;

Where u is 2 to 2.99, t is 2 to 0.01, and s is 0 to 4, and / or aluminum phosphite [Al (H ₂ PO ₃ ) ₃ ], secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], basic aluminum biphosphite [Al (OH) (H ₂ PO ₃ ) ₂ * 2aq], aluminum tetraphosphite [Al ₂ (HPO ₃ ) ₃ * 4aq], aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) _1.5 * 12H ₂ O, Al ₂ (HPO ₃ ) ³ * xAl ₂ O ₃ * nH ₂ O, where x = 2.27 to 1 and / or Al ₄ H ₆ P ₁₆ O ₁₈ .

Preferred inorganic phosphonates (component F) are salts that are insoluble or sparingly soluble in water.

Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts.

More preferably, component F is a reaction product of phosphorous acid and an aluminum compound.

Particularly preferred components F are aluminum phosphites with CAS numbers of 119103-85-4, 220689-59-8, 56287-23-1, 156024-71-4 and 71449-76-8.

The preferred aluminum phosphite is prepared by reacting an aluminum source with a phosphorus source and an optional template in a solvent at a temperature of 20 to 200 ° C. for a period of up to 4 days. For this purpose, the aluminum source and the phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or under reflux, filtered, washed and dried, for example at 110 ° C.

Preferred sources of aluminum are aluminum isopropoxide, aluminum nitrate, aluminum chloride, and aluminum hydroxide (e.g., pseudoboehmite).

Preferred phosphorus sources are phosphorous acid, (acid) ammonium phosphite, alkali metal phosphite or alkaline earth metal phosphite.

Preferred alkali metal phosphites are disodium phosphite, disodium phosphite, trisodium phosphite, and potassium hydrogen phosphite.

The preferred disodium hydrate is Brüggolen ^® H10 by Brüggemann.

Preferred templating agents are 1,6-hexanediamine, guanidine carbonate or ammonia.

The preferred alkaline earth metal phosphite is calcium phosphite.

The preferred ratio of aluminum to phosphorus and solvent is 1: 1: 3.7 to 1: 2.2: 100 on a molar basis. The ratio of aluminum to template is 1: 0 to 1:17 on a molar basis. The preferred pH of the reaction solution is 3 to 9. The preferred solvent is water.

In this case, it is particularly preferred to use a salt of a phosphinic acid that is the same as a salt of phosphorous acid, ie, for example, aluminum diethyl phosphinate together with aluminum phosphite or zinc diethyl phosphinate and phosphorous acid Zinc together.

In a preferred embodiment, the flame-retardant polyamidoamine composition includes a compound of formula (III) as component F.

Wherein Me-based Fe, TiO _r, Zn, or especially Al,
o is 2 to 3, preferably 2 or 3, and
r = (4-o) / 2.

Compounds of the formula III which are preferably used are those in which Me ^{o +} is Zn ²⁺ , Fe ³⁺ or especially Al ³⁺ .

The content of the component F is preferably 0.005% to 10% by weight, especially 0.02% to 5% by weight, based on the total amount of the polyamide composition.

The flame retardant polyamide composition of the present invention has a high heat distortion temperature (HDT-A) according to DIN EN ISO 75-3 of at least 280 ° C, preferably at least 290 ° C, and more preferably at least 300 ° C.

The flame-retardant polyamidoamine composition of the present invention preferably has a relative tracking index of not less than 500 volts as measured according to the International Electrotechnical Commission standard IEC-60112 / 3.

The flame retardant polyamide composition of the present invention, which is also preferable, is measured according to UL-94, especially on a molded article having a thickness of 3.2 mm to 0.4 mm, and reaches a V-0 rating.

A further preferred flame retardant polyamide composition according to the present invention has a glow wire flammability of not less than 960 ° C, as measured on a molded article having a thickness of 0.75 to 3 mm, in accordance with IEC-60695-2-12. Index (glow wire flammability index).

The polyamide composition of the present invention comprises, as component A, one or more thermoplastic polyamides having a melting point of not less than 290 ° C. Melting points were measured by a differential scanning calorimeter (DSC) at a heating rate of 10 degrees / second.

According to Hans Domininghaus in "Die Kunststoffe und ihre Eigenschaften" [The Polymers and Their Properties], 5th edition (1998), page 14, thermoplastic polyamidene means that the molecular chain has no side branches, or has a different number of longer or more Polyamines with short side branches that soften upon heating and can be formed almost indefinitely.

The preferred polyamides according to the present invention can be prepared by various methods and can be synthesized from very different starting materials, and in specific cases, can be individually modified or can be blended with processing aids, stabilizers or polymers A polymer alloy partner, preferably an elastomer, is modified in combination to obtain a material with specific combined properties. Also suitable are blends of other polymers with a certain proportion, preferably polyethylene, polypropylene, ABS, in which case one or more compatibilizers can be used as required. The properties of polyamides can be improved by adding elastomers, for example in terms of impact resistance, especially in the case where they are reinforced with polyamides. The many possible combinations result in a very large number of products with various properties.

Various procedures are known for the preparation of polyamines, which use different monomer units, various chain transfer agents for establishing the desired molecular weight, or have reactive groups for predetermined work-up according to the desired end product Monomer.

Industrially relevant processes for the preparation of polyamides are usually carried out by polycondensation reactions in the melt. It should also be understood that the polycondensation reaction includes hydrolysis polymerization of lactam.

Polyamido-based semi-crystalline aromatic or semi-aromatic polyamidoamines which are preferably used as component A may be composed of diamines and dicarboxylic acids and / or lactams or corresponding amino acids having at least 5 ring members preparation.

Useful reactants mainly include aromatic dicarboxylic acids, preferably isophthalic acid and / or terephthalic acid or their polyamine-forming derivatives (such as salts), which are used alone or Used in combination with an aliphatic dicarboxylic acid or its polyamine-forming derivative, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, and / Or sebacic acid; and aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, nonane-1,9-diamine, 2,2,4-, and 2,4,4 -Trimethylhexamethylenediamine, iso-diaminodicyclohexylmethane, diaminodicyclohexylpropane, bis (aminomethyl) cyclohexane, phenylenediamine and / or xylene The amine and / or aminocarboxylic acid is preferably aminohexanoic acid or the corresponding lactam. Copolymeramides formed from two or more of these monomers are included.

Also particularly suitable are aromatic and semi-aromatic polyamidoamines, ie compounds having at least some repeating units formed from an aromatic structure. If the heat distortion temperature of the molding mixture or the moldings made therefrom of at least 290 ° C is thus reached, the polymers may optionally be combined with smaller amounts (e.g. up to 20% by weight based on the amount of polyamide). ) Aliphatic polyamidoamines, especially PA 6 and / or PA 6.6 are used in combination.

Preferably suitable are aromatic polyamidoamines based on tolylenediamine and adipic acid; or hexamethylenediamine and ortho- and / or terephthalic acid and optionally elastomers as modifiers The prepared polyamines, such as poly-2,4,4-trimethylhexamethylene p-xylylenediamine or poly-m-phenyleneisophthalamide, the above polyfluorenes Block copolymers of amines with polyolefins, olefin copolymers, ionomers or elastomers chemically bonded or grafted, or with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene Diol). EPDM- or ABS-modified polyamides or copolymers; and polyamides also coagulate during processing ("RIM polyamide system").

In a preferred embodiment, component A is an aromatic or semi-aromatic polyamide or a mixture of two or more aromatic or semi-aromatic polyamides or nylon-6,6 with one or more aromatic or semi-aromatic A mixture of polyamines.

In a preferred embodiment, conventional additives, especially release agents, stabilizers, and / or flow aids can be added to other uses by mixing them in the melt or applying them to the surface. Polymers and thermoplastic polyamides. The starting materials of the thermoplastic polyamidine of component A can be synthesized, for example, from petrochemical raw materials and / or by chemical or biochemical methods from renewable raw materials.

Fillers and / or preferred reinforcements are used as component B, preferably glass fibers. Mixtures of two or more different fillers and / or reinforcements may also be used.

Preferred fillers are based on talc; mica; silicate; quartz; titanium dioxide; wallastonite; kaolin; amorphous silica; nano-grade minerals, better montmorillonite or nano-boehmite; carbonic acid Magnesium; chalk; feldspar; mineral beads filler of glass beads and / or barium sulfate. Particularly preferred are mineral particulate fillers based on talc, wollastonite and / or kaolin.

Also particularly preferred is the use of acicular mineral fillers. According to the present invention, acicular mineral fillers are understood to mean mineral fillers having highly significant acicular characteristics. Acicular wollastonite is preferred. Preferably, the aspect ratio of the mineral is 2: 1 to 35: 1, more preferably 3: 1 to 19: 1, and particularly preferably 4: 1 to 12: 1. The average particle size of the acicular mineral filler as component B according to the present invention is measured by a CILAS particle size meter, preferably less than 20 μm, more preferably less than 15 μm, and particularly preferably less than 10 μm.

Component B is preferably used in accordance with the present invention as a reinforcement. For example, these may be carbon fiber and / or glass fiber based reinforcements.

In a preferred embodiment, the filler and / or the reinforcement can be modified on the surface. It is preferred to use an adhesion promoter or an adhesion promoter system for modification, and more preferably a silane-based adhesion promoter system for modification. Particularly when glass fibers are used, in addition to silane, polymer dispersions, film-forming agents, branching agents, and / or glass fiber processing aids can also be used.

The glass fibers preferably used as component B according to the present invention may be short glass fibers and / or long glass fibers. The short or long glass fibers used may be chopped fibers. Short glass fibers can also be used in the form of ground glass fibers. In addition, glass fibers can also be used in the form of continuous fibers, such as rovings, monofilaments, spun yarns, or threads, or glass fibers can be used in the form of textiles, such as fiberglass woven fabrics, fiberglass braids, or Fiberglass felt.

Prior to the incorporation of a polyamide matrix, the typical fiber length of short glass fibers is in the range of 0.05 to 10 mm, preferably 0.1 to 5 mm. After incorporating the polyamide matrix, the length of the glass fibers is reduced. The typical fiber length of short glass fibers after the addition of a polyamide matrix is in the range of 0.01 to 2 mm, preferably 0.02 to 1 mm.

The diameter of a single fiber can vary over a wide range. The typical diameter of a single fiber ranges from 5 to 20 μm.

The glass fibers may have any desired cross-sectional shape, such as round, oval, n-sided, or irregular cross-sections. Glass fibers having a single or multi-lobed cross section can be used.

Glass fibers can be used in the form of continuous fibers or in the form of cut glass fibers or ground glass fibers.

The glass fiber itself, regardless of its cross-sectional area and length, may be selected from, for example, E glass fiber, A glass fiber, C glass fiber, D glass fiber, M glass fiber, S glass fiber, R glass fiber, and / or ECR glass fiber Especially good are E glass fiber, R glass fiber, S glass fiber and ECR glass fiber. The glass fiber preferably has a certain size, and preferably contains polyurethane as a film-forming agent and amine silane as an adhesion promoter.

The E glass fiber used by Xigao has the following chemical composition: SiO ₂ 50 to 56%; Al ₂ O ₃ 12 to 16%; CaO 16 to 25%; MgO ≤ 6%; B ₂ O ₃ 6 to 13%; F ≤ 0.7%; Na ₂ O 0.3 to 2%; K ₂ O 0.2 to 0.5%; Fe ₂ O ₃ 0.3%.

The best R glass fiber used has the following chemical composition: SiO ₂ 50 to 65%; Al ₂ O ₃ 20 to 30%; CaO 6 to 16%; MgO 5 to 20%; Na ₂ O 0.3 to 0.5%; K ₂ O 0.05 to 0.2%; Fe ₂ O ₃ 0.2 to 0.4%; TiO ₂ 0.1 to 0.3%.

Particularly preferred ECR glass fibers used have the following chemical composition: SiO ₂ 57.5 to 58.5%; Al ₂ O ₃ 17.5 to 19.0%; CaO 11.5 to 13.0%; MgO 9.5 to 11.5.

The salt of diethylphosphinic acid used as component C according to the present invention is a known flame retardant for polymerized molding mixtures.

Salts of diphosphinate and phosphonate diethylphosphinic acid which are used as components D and E according to the invention in some amounts are also known flame retardants. A method of making such a combination of substances is described, for example, in US 7,420,007 B2.

The salt of diethylphosphinic acid of component C used according to the present invention may contain a small amount of the salt of component D and the salt of component E, for example, a group of up to 10% by weight based on the content of components C, D and E Component D, preferably 0.01 to 6% by weight, particularly 0.2 to 2.5% by weight, and component E of up to 10% by weight, preferably 0.01 to 6% by weight, especially 0.2% by weight To 2.5% by weight.

The salt of ethylphosphonic acid used according to the invention as component E is likewise known as an additive for diethylphosphinate in flame retardants of polymeric moulding mixtures (for example from WO 2016/065971 A1).

In a further preferred embodiment, the components C, D, E and F are in the form of particles, wherein the median particle size (d ₅₀ ) is 1 to 100 μm.

Preferably, the salt of diethylphosphinic acid used according to the invention as component C is prepared by the method described in DE 103 59 815 A1.

The polyamide composition of the present invention may further contain other additives as component G. The preferred component I in the context of the present invention is an antioxidant, a UV stabilizer, a gamma stabilizer, a hydrolysis stabilizer, a co-stabilizer for an antioxidant, an antistatic agent, an emulsifier, a nucleating agent, and a plasticizer. , Processing aids, impact modifiers, dyes, pigments and / or flame retardants other than components C, D, E and F.

Other additives are known per se as additives to the polyamide composition, and can be used alone or in the form of a mixture or a masterbatch.

The above components A, B, C, D, E and optionally F and / or G can be processed in various combinations to obtain the flame-retardant polyamidoamine composition of the present invention. For example, the components may be mixed into the polyamide melt at the beginning or end of the polycondensation or in a subsequent mixing operation. In addition, there are processing operations where individual components are added at a later stage. This is especially the case with pigments or additive masterbatches. The components, especially those in powder form, can also be applied to polymer pellets by using a drum, which may be warmed by the drying operation.

It is also possible to combine two or more components in the polyamide composition of the present invention in a mixed manner before adding them to the polyamide matrix. Conventional mixing units can be used here, in which the components are mixed in a suitable mixer, for example 0.01 to 10 hours at 0 to 300 ° C.

It is also possible to use two or more components in the polyamide composition of the present invention to prepare pellets, and then add the pellets to a polyamide matrix.

To this end, two or more components in the polyamide composition of the present invention may be processed with a granulating aid and / or a binder in a suitable mixer or disc granulator to obtain pellets. .

The crude product formed initially can be dried or heat treated in a suitable dryer to further increase the particle size.

In a specific example, the polyamide composition of the present invention or two or more components thereof can be manufactured by roll compaction.

In a specific example, the polyamide composition of the present invention or two or more components thereof can be mixed, extruded, shredded (and optionally crushed and classified), and dried ( And optionally coated).

In a specific example, the polyamide composition of the present invention or two or more components thereof can be manufactured by a spray granulation method.

The flame-retardant polymer molding mixture of the present invention is preferably in the form of pellets, such as in the form of an extrudate or a mixture. The granulated material is preferably cylindrical, bead-shaped, cushion-shaped, cube-shaped, rectangular parallelepiped-shaped, or prismatic with round, oval or irregular cross-section.

Typical aspect ratios of granular materials are 1:50 to 50: 1, preferably 1: 5 to 5: 1.

The diameter of the granulated material is preferably 0.5 to 15 mm, more preferably 2 to 3 mm, and the length is preferably 0.5 to 15 mm, more preferably 2 to 5 mm.

The present invention also provides a molded article produced from the above-mentioned flame-retardant polyamine composition containing components A, B, C, D, and E and optionally components F and / or G.

The moldings of the present invention can be in any desired shape and form. Examples of these are fibers, films or shaped articles obtained from the flame-retardant polyamide molding compound of the present invention by any desired molding method, in particular by injection molding or extrusion.

The flame-retardant polyamide molded article of the present invention can be manufactured by any desired molding method. Examples of these methods are injection molding, pressing, foam injection molding, internal gas pressure injection molding, blow molding, film casting, calendaring, lamination, or coating using flame-retardant polyamine molding mixtures at higher temperatures. .

The molded article is preferably an injection molded article or an extruded article.

The flame-retardant polyamidoamine composition of the present invention is suitable for manufacturing fibers, films, and molded articles, and is particularly used in the fields of electrical appliances and electronic appliances.

The present invention preferably relates to the use of the flame-retardant polyamide composition of the present invention in the following applications: plug connectors, current carrying components of power distributors (residual current protection), printed circuit boards, potting compounds ), Power connectors, circuit breakers, lamp covers, LED covers, capacitor covers, coil components and ventilation ducts, ground contacts, plugs, online / online printed circuit boards, plug housings, cables, flexible circuit boards, mobile phone charging cables , Hood or textile coating.

The present invention is also preferably related to the use of the flame-retardant polyamide composition of the present invention for the manufacture of molded articles in the following forms: the form of components in the electrical / electronic field, especially for printed circuit boards, housings, films, Wires, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, rectifiers, memory elements, and sensors; large-area components, especially the housing of the switch box Components; and in the form of components of complex configurations with demanding geometries.

The wall thickness of the shaped articles according to the invention can generally be as high as 10 mm. Particularly suitable shaped objects are shaped objects with a wall thickness of less than 1.5 mm, more preferably less than 1 mm, and particularly preferably less than 0.5 mm.

The following examples illustrate the invention without limiting it.

Used components

Polyamines for industrial use (component A):
Nylon to 6T / 6,6 (melting range 310 to 320 ° C): Vestamid® HT plus 1000 (Evonik)
Nylon-6T / 6I (amorphous): Grivory® G21, (EMS)

Glass fiber (component B):
PPG HP 3610 fiberglass, 10 µm diameter, 4.5 mm length (from PPG, NL)

Flame retardant FM 1 (components C, D and E):
Aluminum salt of diethylphosphinic acid prepared according to Example 3 of US 7,420,007 B2, containing 0.9 mole% aluminum ethylbutylphosphinate and 0.5 mole% aluminum ethylphosphonate

Flame retardant FM 2 (components C, D and E):
Aluminum salt of diethylphosphinic acid prepared according to Example 4, US 4,420,007 B2, containing 2.7 mole% aluminum ethylbutylphosphinate and 0.8 mole% aluminum ethylphosphonate

Flame retardant FM 3 (components C, D and E):
Aluminum salt of diethylphosphinic acid prepared according to the method of US 7,420,007 B2 containing 0.5 mole% aluminum ethylbutylphosphinate and 0.05 mole% aluminum ethylphosphonate

Flame retardant FM 4 (components C, D and E):
Aluminum salt of diethylphosphinic acid prepared according to the method of US 7,420,007 B2 containing 10 mole% aluminum ethylbutylphosphinate and 5 mole% aluminum ethylphosphonate

Flame retardant FM 5 (component C):
Aluminum salt of diethylphosphinic acid prepared in a manner similar to Example 1 of DE 196 07 635 A1

Flame retardant FM 6 (components C and E):
Aluminum salt of diethylphosphinic acid containing 8.8 mole% aluminum ethylphosphonate prepared according to Example 2 of DE 10 2010 018 864 A1

Flame retardant FM 7 (component F):
Aluminum salt of phosphonic acid prepared according to Example 1 of DE 102011120218 A1

2. Manufacturing, processing and testing of flame-retardant polyamide molding compounds

The flame retardant components are mixed with each other in the ratio specified in the table, and added through a side feed port of a twin screw extruder (ZSE27 / 44D of Leistritz) at a temperature of 310 to 330 ° C. Glass fiber was added through the second side feed port. The homogeneous polymer strands were drawn out, cooled in a water bath, and then pelletized.

After sufficiently drying, the molding mixture was processed on an injection molding machine (Arburg 320 C Allrounder) at a melting temperature of 300 to 320 ° C to test the test piece, and the UL 94 test method (Underwriter Laboratories) was used to test and classify the flame retardancy . Not only the classification, but also the afterflame time.

The relative tracking index of the molded article is measured according to the International Electrotechnical Commission standard IEC-60112 / 3.

Glow wire flammability index (GWIT index) is measured according to the standard IEC-60695-2-12.

The heat distortion temperature (HDT) is determined according to DIN EN ISO 75-3.

When measuring the HDT of a molded article, a standard test piece having a rectangular cross section was subjected to a three-point bending test under a constant load. According to the height of the test piece, in order to achieve the so-called edge fiber tension σ _{f of} 1.80 (Method A), 0.45 (Method B) or 8.00 N / mm ² (Method C), the method code and / or spring Apply force. Thereafter, the stressed sample was heated at a constant heating rate of 120 K / h (or 50 K / h). If the bending of the sample reaches an edge fiber tension of 0.2%, the corresponding temperature is equivalent to the HDT value.

The x-ray spectrum (x-ray powder diffraction pattern, "XRD value") of the polyamide composition was analyzed with an x-ray powder diffractometer (X`Pert-MPD from Phillips). The sample was irradiated with Cu-K-α radiation, and the step time was 1 second.

Unless otherwise specified, all tests in individual series are performed under the same conditions (such as temperature program, screw geometry, and injection molding parameters) for comparison.

Examples 1 to 5 and Comparative Examples C1 to C3 with PA 6T / 6,6

The examples cited in the following list show the experimental results of PA 6T / 6,6 molding compounds. All amounts are stated in weight% and are based on a polyamide molding compound that includes flame retardants and reinforcements.

The polyamidoamine compositions of Examples 1 to 5 achieved UL94 V-0 fire rating at 0.4 mm, and had CTI 600 volts, GWFI 960 ° C, and HDT-A 290 ° C. The addition of component F in Example 5 resulted in a further improvement in the flame retardancy exhibited by the shortened afterflame time.

The omission of component D in Comparative Example C1 not only results in a longer afterburning time than in Examples 1 to 4, but also results in lowered CTI, GWFI, and HDT / A values.

In Comparative Example V2, compared with Example V1, the concentrations of components C and E were increased to achieve an improvement in afterflame time. However, compared to Example 2, the polyamidoamine composition still has a lower GWFI value.

The omission of components D and E in Comparative Example C3 not only results in a longer afterflame time than in Examples 1 to 4, but also results in reduced CTI values, GWFI, and HDT / A values.

Examples 6 to 10 and Comparative Examples C4 to C6 using PA 6T / 6I

The examples cited in the following list show the experimental results of PA 6T / 6I molding compounds. All amounts are stated in weight% and are based on a polyamide molding compound that includes flame retardants and reinforcements.

The polyamide compositions of the present invention of Examples 6 to 10 achieved a UL94 V-0 fire rating at 0.4 mm, and had CTI 600 volts, GWFI 960 ° C, and HDT-A 300 ° C. The addition of component F in Example 10 resulted in a further improvement in the flame retardancy exhibited by the shortened afterflame time.

The omission of component D in Comparative Example C4 not only caused a longer afterflame time than Examples 6 to 9, but also caused reduced HDT-A, GWFI, and CTI values.

In Comparative Example V5, compared with Example V4, the concentrations of components C and E were increased to achieve an improvement in the afterburning time. However, this polyamide composition still has lower HDT-A and GWFI values than Example 7.

The omission of components D and E in Comparative Example C6 not only caused a longer afterflame time than those of Examples 6 to 9, but also caused reductions in HDT-A, GWFI, and CTI values.

Claims (17)

A flame retardant polyamide composition comprising:-Polyamine having a melting point of not less than 290 ° C as component A,-Filler and / or reinforcement as component B,-phosphinic acid of formula (I) Salt as component C, Where R ₁ and R ₂ are ethyl, M is Al, Fe, TiO _p or Zn, m is 2 to 3, and p = (4-m) / 2-selected from ethyl butyl phosphinic acid and dibutyl A compound of the group consisting of Al, Fe, TiO _p, and Zn salts of a phosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, and / or dihexylphosphinic acid as component D, and A phosphonate of formula (II) is used as component E, Wherein R ₃ is ethyl, Met is Al, Fe, TiO _q or Zn, n is 2 to 3, and q = (4-n) / 2, and the x-ray powder diffraction pattern of the composition contains the following reflections: In the angle range 2θ from 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 ° and / or in the angle range 2θ from 5.112 ° to 5.312 °, from 6.097 ° to 6.297 °, from 10.082 ° to 10.282 °, from 10.350 ° to 10.550 ° and from 12.308 ° to 12.508 ° and / or in the angle range 2θ from 9.117 ° to 9.317 ° and from 18.537 ° to 18.737 ° and / or in the angle range 2θ from 8.300 ° to 8.500 °. For example, the flame retardant polyamine composition of the scope of application for the patent, the x-ray powder diffraction pattern of the flame retardant polyamine composition contains the following reflections: from 9.099 ° to 9.442 ° in the angle range 2θ, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 °. For example, the flame-retardant polyamidoamine composition of at least one of the items 1 and 2 of the application scope, wherein M and Met are Al, m and n are 3, and component D is an aluminum salt. For example, the flame-retardant polyamidoamine composition of at least one of the scope of application for patents 1 to 3, wherein -The proportion of component A is 25% to 95% by weight, -The proportion of this component B is 1% to 45% by weight, -The proportion of this component C is 1% to 35% by weight, -The proportion of this component D is 0.01% to 3% by weight, and -The proportion of this component E is 0.001% to 1% by weight, The percentage is based on the total amount of the polyamide composition. For example, the flame retardant polyamine composition of the scope of application for patent No. 4 -The proportion of this component A is 25% to 75% by weight, -The proportion of this component B is 20% to 40% by weight, -The proportion of this component C is 5 to 20% by weight, -The proportion of this component D is 0.05% to 1.5% by weight, and -The proportion of this component E is from 0.01% to 0.6% by weight. For example, the flame-retardant polyamidoamine composition of at least one of items 1 to 5 of the patent application scope, wherein the polyamidoamine composition further comprises an inorganic phosphonate as the component F. For example, the flame retardant polyamidoamine composition of the scope of application for patent No. 6 wherein the inorganic phosphonate is a compound of formula (III) Wherein Me-based Fe, TiO _r, Zn, or especially Al, o lines 2-3, and r = (4-o) / 2, wherein the content of the compound of formula (III) to the composition of the polyamide The total amount is 0.005 to 10% by weight, especially 0.02 to 5% by weight. For example, if the flame retardant polyamidoamine composition of at least one of the items in the scope of patent application is applied, the relative tracking index measured by the International Electrotechnical Commission standard IEC-60112 / 3 is not less than 500 volts. For example, the flame retardant polyamidoamine composition of at least one of items 1 to 8 of the patent application scope has a V-0 rating of 3.2 mm to 0.4 mm according to UL94. For example, the flame-retardant polyamidoamine composition of at least one of the items 1 to 9 of the scope of application for a patent, which has a glow wire flammable at a thickness of 0.75 to 3 mm of not less than 960 ° C according to IEC-60695-2-12 (Wire glow flammability). For example, the flame retardant polyamidoamine composition of at least one of items 1 to 10 of the patent application range, the heat distortion temperature HDT-A according to DIN EN ISO 75-3 is at least 280 ° C, preferably at least 300 ° C. For example, the flame-retardant polyfluorene composition of at least one of items 1 to 11 of the application scope, wherein component A is an aromatic or semi-aromatic polyfluorene or two or more kinds of aromatic or semi-aromatic polyfluorene A mixture of amines or a mixture of nylon-6,6 and one or more aromatic or semi-aromatic polyamines. For example, the flame-retardant polyfluorene composition according to item 12 of the patent application, wherein component A is an aromatic or semi-aromatic polyfluorene or a mixture of two or more aromatic or semi-aromatic polyamines. For example, a flame-retardant polyamidoamine composition of at least one of items 1 to 13 of the patent application scope, wherein glass fiber is used as the component B. For example, the flame-retardant polyamine composition of at least one of items 1 to 14 of the application scope, wherein components C, D, E and optionally F are in the form of particles, wherein the median value of these components Median particle size d ₅₀ is 1 to 100 µm. For example, the flame retardant polyamidoamine composition of at least one of the scope of claims 1 to 15 of the patent application further includes other additives as component G, wherein the other additives are selected from the group consisting of: antioxidants , UV stabilizers, g-ray stabilizers, hydrolysis stabilizers, co-stabilizers for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, Other flame retardants than pigments and / or components C, D, E and F. A use of the polyamide composition according to any one of claims 1 to 16 of the scope of application for a patent, which is used for manufacturing fibers, films, and shaped bodies, especially for applications in the electrical and electronic fields.