EP0000540B1 - Masses à mouler en polyamide ignifugées - Google Patents

Masses à mouler en polyamide ignifugées Download PDF

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Publication number
EP0000540B1
EP0000540B1 EP78100434A EP78100434A EP0000540B1 EP 0000540 B1 EP0000540 B1 EP 0000540B1 EP 78100434 A EP78100434 A EP 78100434A EP 78100434 A EP78100434 A EP 78100434A EP 0000540 B1 EP0000540 B1 EP 0000540B1
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EP
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Prior art keywords
weight
phenol
contain
polyamide moulding
compositions according
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Application number
EP78100434A
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German (de)
English (en)
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EP0000540A1 (fr
Inventor
Peter Dr. Tacke
Dieter Dr. Neuray
Dietrich Dr. Michael
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Bayer AG
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Bayer AG
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Priority claimed from DE19772734103 external-priority patent/DE2734103A1/de
Priority claimed from DE19772754491 external-priority patent/DE2754491A1/de
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Publication of EP0000540A1 publication Critical patent/EP0000540A1/fr
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Definitions

  • the present invention relates to flame-retardant, preferably reinforced and / or filled polyamide molding compositions which contain a combination of powdered red phosphorus and phenol-aldehyde resin as fire retardants.
  • red phosphorus is a very effective fire protection agent for glass fiber reinforced polyamides, while it does not have a fire protection effect or does accelerate the burning process in the case of unreinforced polyamides.
  • Dust explosions are avoided by using the finely divided phosphorus in the form of concentrates, for example as caprolactam concentrates, as described in DAS 1 965 635, or by coating or coating it with synthetic resins. Wrapping methods can be found in DE-OS 2 408 488 and 2 428 758.
  • the coverage of the red color of the phosphor requires 2 to 5 times the amount by weight of commercially available Tio 2 pigments or 6 to 10 times the weight of ZnS.
  • Ti0 2- contents of 15-30% by weight reduce the tough elastic properties of the molding compositions to such an extent that they can no longer be used for technical use.
  • Flame-resistant polyamide molding compositions which contain 10-40% by weight, preferably 15-35% by weight, based on the total molding composition, of reinforcing and / or fillers are particularly preferred.
  • Phenol-aldehyde resins in the sense of the invention are resins from phenols and formaldehyde and / or acetaldehyde which soften in the range from -30 to + 350 ° C., preferably condensed in an acid medium.
  • the phenol-aldehyde condensation resins are prepared by known methods, as described, for example, in Houben-Weyl, Methods of Organic Chemistry, volume 14/2, 4th edition, p. 273 f. are described.
  • the molar ratio of aldehyde to the phenolic compound is in the. Usually in the range 0.3-1.2, preferably in the range 0.5-0.9.
  • the novolaks obtained by acid condensation are preferably used.
  • the phenol-aldehyde resin can be crosslinked, for example with boric acid, phosphoric acid, phosphorous acid, esters of phosphorous and phosphoric acid. polyvalent carboxylic acids, polyfunctional isocyanates, polyfunctional epoxides or PCI 3 . Up to 25% by weight crosslinking agent can be added to the resin. Crosslinking with polyfunctional epoxides, phosphoric acid and boric acid is particularly effective.
  • the phenol-aldehyde resin should preferably have a minimum melt viscosity of 20 Pa.s at 200 ° C.
  • the conversion of the phenol-aldehyde resins into metal salts can be advantageous, because this usually improves the effectiveness of the fire protection combinations.
  • Possible metals for salt formation are: alkali metals, alkaline earth metals, zinc, cadmium, tin, lead, antimony, aluminum, copper, manganese, iron, cobalt, nickel.
  • the resins may contain one or more of the metals.
  • the metal salts can be prepared, for example, from the phenol-aldehyde resins and the oxides, hydroxides, carbonates, acetates, formates, phosphates, borates of the metals. Up to 15% by weight of these metal compounds, preferably the oxides, can be added to the resins.
  • the phenol-aldehyde resins can also be grafted onto the polyamide component of the molding compositions according to the invention if, for example, the crosslinking agent (for example a diepoxide) has not reacted with the resin or has not reacted fully, and therefore still during the incorporation of the fire retardants into the polyamides can react with the polyamide.
  • the crosslinking agent for example a diepoxide
  • polyamides for the molding compositions according to the invention: PA-6, PA-6,6, their mixtures, block polyamides and copolymers of e-caprolactam, adipic acid, hexamethylenediamine, furthermore PA-1 and PA-12 and polyamides which consist of aliphatic diamines and adipic acid and / or isophthalic acid and / or terephthalic acid and / or sebacic acid and / or azelaic acid and / or cyclohexanedicarboxylic acid.
  • polyamides are suitable, which consist of the aliphatic dicarboxylic acids and aromatic diamines such as e.g. m- and p-phenylenediamine are produced, as well as polyamide mixtures and copolyamides from all the components mentioned, insofar as aliphatic and partially aliphatic polyamides are formed.
  • Preferred polyamides are aliphatic polyamides, in particular PA-6 and PA-6,6.
  • the average diameter of the phosphor particles in the concentrate rates is ⁇ 200 ⁇ m, preferably ⁇ 100 ⁇ m, particularly preferably ⁇ 20 ⁇ m. All commercially available, colored allotropic forms of red phosphorus are suitable as phosphorus for the fire protection agent mixture according to the invention.
  • the powdered red phosphorus can preferably be stirred or kneaded into the molten resin.
  • the resin can also be mixed with the phosphorus in powder form and a granulate or pills can be pressed from the mixture, optionally under the action of heat.
  • the resin can also be condensed from its starting components in the presence of phosphorus.
  • the development of toxic phosphorus-hydrogen compounds is particularly low.
  • the release of such phosphines can be suppressed even further by adding small amounts of MoS 2 , HgO, Pb0 2 , CuO, ZnO.
  • the fire protection agent mixtures or concentrates according to the invention can be incorporated into the polyamides, optionally together with pigments and other additives, in commercially available machines. Single-shaft and double-shaft extruders are preferred.
  • Pigments for covering the red inherent color of the phosphor and for setting a specific color can either be present in the concentrates according to the invention in addition to the phosphor or can be incorporated into the molding compositions simultaneously with the concentrates according to the invention or separately.
  • Preferred white pigments to cover the red inherent color of the phosphor are: Ti0 2 , ZnS, BaS0 4 . 2-10 times, preferably 3-5 times, the amount of phosphorus of white pigments contained in the molding compositions is used.
  • the person skilled in the art is aware of the amounts of additional pigments that can be used to set certain shades.
  • Color pigments, dyes, processing aids and stabilizers which may be present in the usual amounts in the molding compositions according to the invention include to name the following: carbon black, cadmium sulfide, phthalocyanines, salts of stearic acid, talc, sterically hindered phenols.
  • reinforcing and fillers which can be contained in the molding compositions according to the invention, i.a. to name the following: glass, asbestos fibers, glass balls, talc, wollastonite, microvit, chalk, quartz, fibers, in particular glass fibers, are preferred as reinforcing materials.
  • the molding compositions according to the invention can be processed to flame-resistant molded parts on commercially available injection molding machines.
  • mixtures I-XIII in polyamide-6,6, which had a relative solution viscosity, measured with a 1% strength solution in m-cresol at 25 ° C., of 3.03, optionally with pigments and auxiliaries, is carried out in one Single-screw extruders from Reifen Reifenberger with a screw diameter D of 30 mm and a screw length of 20 D.
  • the compositions, the working-in conditions and the fire behavior of the mixtures are shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (9)

1. Matières à mouler en polyamide, qui contiennent 0,5 à 25% en poids, par rapport à la matière à mouler totale, d'un mélange conférant l'ininflammabilité de phosphore rouge en particules de grosseur moyenne inférieure à 200 µm et de résines phénol-aldéhyde ainsi que, le cas échéant, des matières de renforcement et/ou des charges, caractérisées en ce qu'elles contiennent un mélange de:
a) 55 à 95% en poids de résines phénol-aldéhyde
b) 5 à 45% en poids de phosphore rouge.
2. Matières à mouler en polyamide suivant la revendication 1, caractérisées en ce qu'elles contiennent 3 à 12% en poids du mélange.
3. Matières à mouler en polyamide suivant lés revendications 1 et 2, caractérisées en ce que le mélange est formé de 60 à 80% en poids du composant a) et de 20 à 40% en poids du composant b).
4. Matières à mouler en polyamide suivant les revendications 1 à 3, caractérisées en ce qu'elles contiennent 10 à 40% en poids, par rapport à la matière à mouler totale, de matières de renforcement et/ou de charges.
5. Matières à mouler en polyamide suivant les revendications 1 à 4, caractérisées en ce qu'elles contiennent des novolaques comme résines phénol-aldéhyde.
6. Matières à mouler en polyamide suivant les revendications 1 à 5, caractérisées en ce que les résines de condensation phénol-aldéhyde contiennent jusqu'à 25% en poids d'agent de réticulation.
7. matières à mouler en polyamide suivant les revendications 1 à 5, caractérisées en ce que des composés métalliques sont ajoutés aux résines de condensation phénol-aldéhyde en proportion allant jusqu'à 15% en poids.
8. Matières à mouler en polyamide suivant la revendication 4, caractérisées en ce qu'elles contiennent des fibres de verre comme matières de renforcement.
9. Matières à mouler claires en polyamide suivant les revendications 1 à 8, caractérisées en ce qu'elles contiennent deux à dix fois la quantité de phosphore, de pigments blancs.
EP78100434A 1977-07-28 1978-07-19 Masses à mouler en polyamide ignifugées Expired EP0000540B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2734103 1977-07-28
DE19772734103 DE2734103A1 (de) 1977-07-28 1977-07-28 Flammfeste polyamidformmassen
DE2754491 1977-12-07
DE19772754491 DE2754491A1 (de) 1977-12-07 1977-12-07 Flammfeste unverstaerkte und ungefuellte polyamidformmassen

Publications (2)

Publication Number Publication Date
EP0000540A1 EP0000540A1 (fr) 1979-02-07
EP0000540B1 true EP0000540B1 (fr) 1981-02-11

Family

ID=25772418

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100434A Expired EP0000540B1 (fr) 1977-07-28 1978-07-19 Masses à mouler en polyamide ignifugées

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EP (1) EP0000540B1 (fr)
DE (1) DE2860466D1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3131447A1 (de) * 1981-08-07 1983-02-24 Basf Ag, 6700 Ludwigshafen Flammfeste polyamid-formmassen
CA1196437A (fr) * 1981-12-19 1985-11-05 Kazushi Hirobe Resine resistant a la progression du feu
DE102004039148A1 (de) * 2004-08-12 2006-02-23 Clariant Gmbh Glühdrahtbeständige flammwidrige Polymere

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2428758C3 (de) * 1974-06-14 1982-05-13 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung selbstverlöschender thermoplastischer Formmassen
FR2314216A1 (fr) * 1975-06-10 1977-01-07 Rhone Poulenc Ind Compositions ignifugees de matieres plastiques
DE2551718B2 (de) * 1975-11-18 1979-08-02 Basf Ag, 6700 Ludwigshafen Brandgeschützte Polyamidformmassen
FR2344615A1 (fr) * 1976-03-19 1977-10-14 Rhone Poulenc Ind Compositions destinees a l'ignifugation de matieres plastiques
FR2367100A1 (fr) * 1976-10-11 1978-05-05 Rhone Poulenc Ind Compositions a base de polyamide ignifuge

Also Published As

Publication number Publication date
DE2860466D1 (en) 1981-03-26
EP0000540A1 (fr) 1979-02-07

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