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WO1996028499A1 - Composition de resine polyamide ignifuge et procede de fabrication de celle-ci - Google Patents

Composition de resine polyamide ignifuge et procede de fabrication de celle-ci Download PDF

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Publication number
WO1996028499A1
WO1996028499A1 PCT/US1996/003427 US9603427W WO9628499A1 WO 1996028499 A1 WO1996028499 A1 WO 1996028499A1 US 9603427 W US9603427 W US 9603427W WO 9628499 A1 WO9628499 A1 WO 9628499A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide resin
melamine cyanurate
resin composition
flame resistant
masterbatch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1996/003427
Other languages
English (en)
Inventor
Atsushi Miyabo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of WO1996028499A1 publication Critical patent/WO1996028499A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a flame resistant polyamide resin composition which has flame resistance, as well as excellent mechanical properties, particularly a mechanical property such as a tensile at the break and elongation, or the like, and a process for the manufacture thereof.
  • polyamide resins are used in various fields such as electrical electronic parts but they are deficient, in general, in flammability for which studies have heretofore been carried out to obtain flame resistant polyamide resins.
  • Methods have previously been used to achieve a flame resistant polyamide resin composition into which are compounded a variety of flame retarders, such as halogen compounds, phosphorus compounds, and the like; in particular, polyamide resin compositions compounded with a melamine cyanurate are known (Japanese Patent Laid Open S53-31759) to provide molded articles with good appearance without generating toxic components on thermal decomposition.
  • the amount of the melamine cyanurates compounded for improving the flame resistance by such melamine cyanurate incorporation are, in general. 5-10% by weight, wherein the greater the amount compounded, the greater the flame resistance.
  • the dispersibility of the melamine cyanurate in the polyamide resin is poorer, so that the flame resistant polyamide resin composition in which such a flame retardant is compounded is inferior in mechanical properties compared with those having no such flame retardant. Therefore, it has been desired to improve mechanical properties, such as tensile elongation, and the like, in particular in electrical and electronic parts applications.
  • the present invention relates to a flame resistant polyamide resin composition obtained by melt-kneading a polyamide resin with a masterbatch obtained by melt-kneading a polyamide resin and a melamine cyanurate, wherein the content of the melamine cyanurate in the composition is 1-30% by weight.
  • the invention also relates to a process for manufacturing a flame resistant polyamide resin composition by melt-kneading a polyamide resin with a melamine cyanurate into a masterbatch and a step of further melt-kneading the masterbatch with a polyamide resin into the composition.
  • Embodiment 1 of this invention is a flame resistant polyamide resin composition
  • a flame resistant polyamide resin composition comprising a composition obtained by melt- kneading a polyamide resin with a masterbatch obtained by melt- kneading a polyamide resin and a melamine cyanurate, wherein the content of the melamine cyanurate in the composition is 1-30% by weight.
  • Embodiment 2 of this invention is a flame resistant polyamide resin composition in embodiment 1 where the content of the melamine cyanurate in the masterbatch is 10-60% by weight.
  • Embodiment 3 of this invention is a process for the manufacture of a flame resistant polyamide resin composition which comprises a step of melt-kneading a polyamide resin with a melamine cyanurate into a masterbatch and a step of further melt- kneading the masterbatch with a polyamide resin into the composition.
  • Embodiment 4 of this invention is a process for the manufacture of a flame resistant polyamide resin composition in embodiment 3 wherein the content of the melamine cyanurate in the masterbatch is 10-60% by weight.
  • Polyamide resins which are used in this invention include polymers obtained by polycondensing diamines, such as hexamethylene diamine and a dicarboxylic acid, such as terephthalic acid, isophthalic acid, and adipic acid; polymers from epsilon-caprolactam, amino caproic acid, enantho lactam, 7-aminoheptanoic acid, alpha-pyrrolidone, and copolymers thereof.
  • a single known polyamide resin such as nylon 66 or nylon 6, a blend of a plurality of resins, or copolymers thereof, preferably nylon 66 and/or nylon 6.
  • the melamine cyanurate which is used in this invention is an equimolar reaction product of cyanuric acid and a melamine, for example, obtained by mixing an aqueous cyanuric acid and an aqueous melamine solution with agitation to allow reaction to take place at a temperature of about 90-100°C, and filtering the precipitate generated.
  • the melamine cyanurate is, in general, a white solid which may be reduced to a fine powder or a commercial powdery product may be used as obtained or after pulverization.
  • the melamine cyanurate used in this invention may have some of its amino or hydroxyl groups substituted with other substituents and the term "melamine cyanurate" referred to in this invention shall include such substituted versions as well.
  • Such melamine cyanurate is preferably contained in this invention in an amount of 1-30% by weight in the final polyamide composition. An amount less than this range can no longer provide the expected flame retardation effect, while an amount exceeding this range will reveal an adverse effect on the mechanical properties, thus making both extremes undesirable.
  • the flame retardant polyamide resin composition of this invention is obtained by first melt kneading the above melamine cyanurate with a polyamide resin, followed by melt kneading the masterbatch with an additional polyamide resin.
  • the flame resistant polyamide composition of this invention has a melamine cyanurate kneaded-in a total of two times, initially at a high concentration and then at a relatively low concentration, to make the dispersion of the melamine cyanurate in the polyamide resin very good. This enables the final product to obtain excellent flame resistance characteristics without reducing the mechanical properties, particularly resulting in suitable products to be used in applications in electrical and electronic parts, and the like.
  • the masterbatch of the composition of this invention is, for example, obtained by kneading 10-60% by weight, preferably 30- 40% by weight of a melamine cyanurate with a polyamide resin.
  • An amount of the melamine cyanurate below this range will not give any advantage of using a masterbatch, while an amount exceeding this range will cause manufacturing problems, such as a difficulty in dispersion and the occurrence of strand breakage during manufacturing. In addition, it will have a tendency to show reduced mechanical properties.
  • Such a masterbatch may be compounded with additives, such as a dispersion agent, a heat stabilizer, an antiweathering agent, a slip agent, a colorant, a filler. an antistatic agent, or the like.
  • the melamine cyanurate may be pre-blended with the polyamide or else may be separately fed to the extruder from independent hoppers, or else from a side feeder, either of which may be used in combination, but the consideration of workability and safe feeding makes it preferable to feed from a side feeder.
  • the kneading is carried out using an extruder, or the like, at a temperature at which the polyamide resin used melts.
  • the masterbatch thus manufactured is then further uniformly mixed with a polyamide resin for melt-kneading to give a flame resistant polyamide composition.
  • the aforementioned additives may be added at this stage or may be added at this stage additionally to a masterbatch to which some additives have already been added.
  • the compounding ratio of the masterbatch and the polyamide resin should be one to be within the above range for the compounding ratio of the melamine cyanurate.
  • the polyamide resin used here may not necessarily be the same polyamide resin which is compounded in the masterbatch, as long as it can give finally a uniform flame resistant polyamide resin composition.
  • the flame resistant polyamide resin composition of this invention has the melamine cyanurate as described above obtained by a two-step kneading for it to be compounded in the polyamide resin so that it provides good dispersibility even at a high compounding level of the melamine cyanurate, so as to give a flame resistant polyamide resin composition having good mechanical properties.
  • a flame resistant polyamide resin composition containing a melamine cyanurate the use of a method of first kneading a melamine cyanurate initially at a high concentration into a polyamide resin followed by kneading with an additional polyamide resin can give a polyamide resin composition which has good mechanical properties and excellent flame resistance.
  • Nylon 66 Zytel® resin manufactured by the DuPont Company.
  • Flammability and mechanical properties were measured on each test piece as given below with the results listed in Table 1. Measurements were made according to ASTM D-638-58T for elongation, ASTM D-638 for tensile strength, and ASTM D-256 for notched Izod impact strength. Flammability was measured using a 1/32 inch (about 0.8 mm) test piece according to UL94.
  • Nylon 66 and melamine cyanurate similar to those used in the above examples, were preblended for ten minutes by a Henschel mixer to bring the melamine cyanurate content to 5, 8, and 9% by weight, followed by melt kneading each blend further by a twin screw extruder (manufactured by W&P Company, ZSK-40) into pellets.
  • Each pelletized product was molded by an injection molder (Sumitomo Nestarl [Phonetic Translation]) into test pieces on which elongation and flammability were measured in a manner similar to that of the above examples.
  • the present invention which generates a polyamide resin composition by kneading melamine cyanurate into a polyamide resin in two steps, so that the dispersibility of the melamine cyanurate is good, gives a molded article from such a composition that retains good mechanical properties with improved flame resistance, which is particularly good for use in electrical and electronic parts.

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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)

Abstract

L'invention concerne une composition de résine polyamide ignifuge avec une résistance à la rupture par traction et un allongement à la rupture améliorés, ainsi qu'un procédé pour la fabriquer. La résine polyamide est malaxée à chaud avec un mélange maître obtenu en malaxant à chaud une résine polyamide avec un cyanurate de mélamine pour donner une composition de résine polyamide avec 1-30 % en poids de cyanurate de mélamine.
PCT/US1996/003427 1995-03-13 1996-03-13 Composition de resine polyamide ignifuge et procede de fabrication de celle-ci Ceased WO1996028499A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5264195A JPH08245875A (ja) 1995-03-13 1995-03-13 難燃性ポリアミド樹脂組成物およびその製造方法
JP7/52641 1995-03-13

Publications (1)

Publication Number Publication Date
WO1996028499A1 true WO1996028499A1 (fr) 1996-09-19

Family

ID=12920468

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/003427 Ceased WO1996028499A1 (fr) 1995-03-13 1996-03-13 Composition de resine polyamide ignifuge et procede de fabrication de celle-ci

Country Status (2)

Country Link
JP (1) JPH08245875A (fr)
WO (1) WO1996028499A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1676877A1 (fr) * 2004-12-28 2006-07-05 Campine N.V. Composition de polyamide et/ou polyester inimflammable et procedure de cette preparation
DE10144231B4 (de) * 2001-09-10 2008-06-05 Lanxess Deutschland Gmbh Mit organischen Verbindungen behandeltes Melamincyanurat, Verfahren zu dessen herstellung sowie dessen Verwendung als Flammschutzmittel in Kunststoffen

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4201383B2 (ja) * 1998-04-22 2008-12-24 旭化成ケミカルズ株式会社 難燃性ポリアミド樹脂成形材料
JP2001110241A (ja) * 1999-10-13 2001-04-20 Ube Ind Ltd ワイヤハーネス

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4127112C1 (en) * 1991-08-16 1992-08-27 Lehmann & Voss & Co, 2000 Hamburg, De Fire retardant concentrate for thermoplastics - contains polyamide or polyurethane, adduct of melamine cyanarate and hydrophilic silicic acid, and flow improver etc.
DE4314853A1 (de) * 1993-05-05 1994-11-10 Gerhard Dr Pohl Flammhemmende thermoplastische Kunststoffe
WO1995004359A1 (fr) * 1993-08-03 1995-02-09 T & N Technology Limited Revetements protecteurs pour des revetements isolants sur des fils electriques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4127112C1 (en) * 1991-08-16 1992-08-27 Lehmann & Voss & Co, 2000 Hamburg, De Fire retardant concentrate for thermoplastics - contains polyamide or polyurethane, adduct of melamine cyanarate and hydrophilic silicic acid, and flow improver etc.
DE4314853A1 (de) * 1993-05-05 1994-11-10 Gerhard Dr Pohl Flammhemmende thermoplastische Kunststoffe
WO1995004359A1 (fr) * 1993-08-03 1995-02-09 T & N Technology Limited Revetements protecteurs pour des revetements isolants sur des fils electriques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10144231B4 (de) * 2001-09-10 2008-06-05 Lanxess Deutschland Gmbh Mit organischen Verbindungen behandeltes Melamincyanurat, Verfahren zu dessen herstellung sowie dessen Verwendung als Flammschutzmittel in Kunststoffen
EP1676877A1 (fr) * 2004-12-28 2006-07-05 Campine N.V. Composition de polyamide et/ou polyester inimflammable et procedure de cette preparation

Also Published As

Publication number Publication date
JPH08245875A (ja) 1996-09-24

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