JP2005336474A - Flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition exhibiting excellent flame retardancy and excellent impact properties. <P>SOLUTION: This flame-retardant resin composition comprises (A) a polyamide resin, (B) a flame-retardant comprising a component B1 comprising a phosphinic acid salt represented by formula (I) and/or a diphosphinic acid salt represented by formula (II) and/or a polymer of these and a component B2 comprising a condensation product of melamine, and/or a reaction product of melamine with phosphoric acid, and/or a reaction product of the condensation product of melamine with phosphoric acid and/or a mixture of these, (C) red phosphorus and (D) an impact-resistant material and (E) an inorganic filler. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant resin composition having excellent flame retardancy and excellent impact characteristics.

Reinforced flame retardant polyamide resin with inorganic filler added to flame retardant polyamide resin, taking advantage of its excellent mechanical properties, electric parts such as automobile parts, power breakers, electromagnetic switches, wiring connectors, electric tools, etc. Widely used.
In the flame-retardant polyamide resin, those containing a triazine compound, a halogen compound, magnesium hydroxide or red phosphorus as a flame retardant are used, but each has a problem.

In a resin composition containing a triazine compound such as melamine cyanurate, generation of ammonia gas, amine-based gas, cyan gas and the like cannot be suppressed during processing or fire. In addition, these compounds are also disadvantageous in that a sufficient flame retardant effect is hardly exhibited in the reinforced polyamide composition and the decomposition temperature is low. (See melamine cyanurate, Patent Document 1. See Melem, Patent Document 2.)
A compound containing a halogen compound has a problem that corrosive decomposition gas is generated at the time of molding, which may corrode the molding machine or the mold, or may generate harmful substances at the time of incineration to contaminate the environment.
Magnesium hydroxide is a non-toxic non-halogen flame retardant, and there are no problems such as toxic gas and corrosion of processing machines. However, a large amount of addition is required to develop sufficient flame resistance. There is a problem that mechanical properties such as impact resistance deteriorate. It is also difficult to obtain a good molded product appearance.
A compound containing a large amount of red phosphorus is not preferable from the viewpoint of safety because red phosphorus may decompose during the molding process to generate toxic phosphine gas. Moreover, there exists a problem that toughness, such as impact resistance, falls by a large amount of compounding.

Further, a flame retardant combination of a phosphinate and a melamine or a melamine compound such as melamine cyanurate or melamine phosphate (see Patent Document 3), a phosphinate and a melamine condensation product or a melamine or melamine condensation product There has also been proposed a flame retardant combination of a reaction product of phosphoric acid (see Patent Document 4).
By blending these flame retardant combinations, flame retardancy is improved, but on the other hand, in order to improve the impact characteristics of polyamide resin, adding flame resistant material further reduces the flame retardancy was there.

JP-A-53-31759 JP 58-45352 A Special Table 2000-508365 JP 2001-72978 A

  An object of the present invention is to solve the above problems and to provide a flame retardant resin composition having excellent flame retardancy and excellent impact characteristics.

The present invention
(A) aliphatic polyamide resin,
(B) As component B1, (B1a) phosphinic acid salt represented by the following formula (I) and / or (B1b) diphosphinic acid salt represented by the following formula (II), and / or (B1a ) And (B1b), and as component B2, (B2a) the condensation product of melamine, or (B2b) the reaction product of melamine and phosphoric acid, or (B2c) the condensation of melamine A flame retardant comprising a reaction product of a product and phosphoric acid, or a mixture comprising at least two of (B2a) to (B2c),
(C) Red phosphorus,
The present invention relates to a flame retardant resin composition comprising (D) an impact resistant material and (E) an inorganic filler.

［式中、Ｒ^１及びＲ^２は、同一か又は異なり、線状もしくは分枝状のＣ_１−Ｃ_６−アルキル及び／又はアリールであり、Ｒ^３は、線状もしくは分枝状のＣ_１−Ｃ_１０−アルキレン、Ｃ_６−Ｃ_１０−アリーレン、Ｃ_６−Ｃ_１０−アルキルアリーレン又はＣ_６−Ｃ_１０−アリールアルキレンであり、Ｍは、カルシウムイオン、マグネシウムイオン、アルミニウムイオン及び／又は亜鉛イオンであり、ｍは、２又は３であり、ｎは、１又は３であり、ｘは、１又は２である。］

[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and R ³ is linear or branched C ₁ -C ₁₀ - _alkylene, C 6 _{-C 10} - _arylene, C 6 _{-C 10} - alkylarylene or _C 6 _{-C 10} - aryl alkylene, M is calcium ions, magnesium ions, aluminum ions and / or zinc ions Wherein m is 2 or 3, n is 1 or 3, and x is 1 or 2. ]

  Since the flame retardant resin composition is excellent in flame retardancy and has excellent impact characteristics, it is used for electric / electronic parts such as automobile parts, machine parts, breaker parts, electric tools, electric connectors, personal computer cases, etc. And is extremely useful as a non-halogen flame retardant resin composition.

The (A) polyamide resin in the present invention is a polyamide mainly composed of aminocarboxylic acid, lactam or diamine and dicarboxylic acid.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 6 to 12 carbon atoms, such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. It is done.
Examples of the lactam include lactams having 6 to 12 carbon atoms, and examples include α-pyrrolidone, ε-caprolactam, ω-laurolactam, and ε-enantolactam.

Examples of diamines include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethyl. Hexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane Bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, metaxylylene Amines, aliphatic such as p-xylylenediamine, alicyclic, and a diamine of the aromatic and the like.
Examples of dicarboxylic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naltalenedicarboxylic acid, etc. Aliphatic, alicyclic and aromatic dicarboxylic acids may be mentioned.

In the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.
Specific examples of the polyamide resin used in the present invention include polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 6/66, polynonamethylene terephthalamide (polyamide 9T). , Polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene terephthalamide / polycaproamide copolymer (polyamide 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide Copolymer (polyamide 66 / 6I), polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 6I / 6), polydodecamide / polyhexamethylene terephthalamide copoly -(Polyamide 12 / 6T), Polyhexamethylene adipamide / Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Polyamide 66 / 6T / 6I), Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Polyamide) 6T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene terephthalamide) copolymer (polyamide 6T / M5T), polyxylylene adipamide (polyamide MXD6), and mixtures or copolymer resins or mixtures thereof Particularly useful are polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12 or polyamide 6 / 6, and the like.

  The blending ratio of the (A) polyamide resin used in the present invention is suitably 30 to 80% by weight, preferably 40 to 60% by weight, based on the entire resin composition. (A) If the blending ratio of the polyamide resin is less than 30% by weight, molding processability is poor and sufficient material properties cannot be obtained, and if it exceeds 80% by weight, sufficient flame retardancy cannot be obtained. It is not preferable.

  As the polyamide resin used in the present invention, a polyamide resin having a polymerization degree within a specific range, that is, a relative viscosity is preferable. A preferred relative viscosity is a value measured according to JIS K 6920 and is in the range of 1.8 to 5.0, particularly preferably 2.0 to 4.5. If the relative viscosity is low, the material strength becomes small. On the other hand, if the relative viscosity is too high, the fluidity is lowered and the moldability and the product appearance may be impaired.

  The flame retardant (B) in the present invention contains, as component B1, (B1a) a phosphinic acid salt represented by the following formula (I) and / or (B1b) a diphosphinic acid salt represented by the following formula (II): And / or a polymer comprising at least one of (B1a) and (B1b), and as component B2, (B2a) a condensation product of melamine, or (B2b) a reaction product of melamine and phosphoric acid, Or (B2c) a reaction product of a condensation product of melamine and phosphoric acid, or a mixture of at least two of (B2a) to (B2c).

In component B1, R ¹ and R ² are preferably the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, particularly preferably the same or different and methyl , Ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

R ³ is linear or branched C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, preferably Methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, or phenylene or naphthylene, or methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene Rene, ethylnaphthylene or tert-butylnaphthylene, or phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

  M is a calcium ion, a magnesium ion, an aluminum ion and / or a zinc ion, preferably an aluminum ion or a zinc ion.

The term “phosphinic acid salt” as used below includes phosphinic acid and diphosphinic acid salts and polymers thereof.
This phosphinate is produced in an aqueous medium and is essentially a monomeric compound. Depending on the reaction conditions, polymer phosphinates having a degree of condensation of 1 to 3 are also included depending on the environment.
Examples of phosphinic acids suitable as components of phosphinates are dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, isobutylmethylphosphinic acid, octylmethylphosphinic acid, methyl-n-propylphosphinic acid, methane-1,2 -Di (methylphosphinic acid), ethane-1,2- (dimethylphosphinic acid), hexane-1,6-di (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methylphenylphosphinic acid and Diphenylphosphinic acid.

  The phosphinic acid salts of the present invention can be prepared by known methods, for example as detailed in EP-A-699708. In this case, the phosphinic acid is produced using, for example, a metal carbonate, a metal hydroxide or a metal oxide in an aqueous solution.

  Component B2 is preferably a (B2a) melamine condensation product, more preferably melem, melam, melon and / or a higher degree of these compounds, or component B2 is preferably (B2b) a reaction product of melamine and phosphoric acid, or (B2c) a condensation product of melamine and phosphoric acid, or a mixture comprising at least two of these (B2a) to (B2c), The reaction products here are preferably dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate and / or mixed polysalts of this kind. Particularly preferred are melamine polyphosphates having a chain length of greater than 2, in particular greater than 10.

  The blending amount of the flame retardant (B) used in the present invention is appropriately 1 to 30% by weight of each of the above components B1 and B2 with respect to the entire resin composition, preferably, 3 to 20% by weight, more preferably 3 to 15% by weight.

  The red phosphorus as the component (C) used in the present invention preferably has an average particle diameter of 1 to 50 μm. In particular, in order to suppress the decrease in mechanical strength and the generation of phosphine, it is preferable that the surface treatment is performed as necessary and the particle surface is smooth, but the presence or absence of the surface treatment, the type of the surface treatment agent, the method of the surface treatment and the particle The surface property is not particularly limited.

  The blending amount of (C) red phosphorus is preferably 1 to 20% by weight, particularly 3 to 10% by weight, based on the entire resin composition. In addition, when the component (C) is less than 1% by weight, it is not preferable because the flame retardancy is not sufficiently imparted, and when it exceeds 20% by weight, problems such as generation of phosphine during production and molding become unfavorable.

  Examples of the impact resistant material which is the component (D) used in the present invention include those generally called rubbers and elastomers. Specific examples thereof include EPR (ethylene / propylene copolymer), EPDM (ethylene・ Olefin elastomers such as propylene / diene copolymer), EBR (ethylene / butene copolymer), EOR (ethylene / octene copolymer), SBS (styrene / butylene / styrene block copolymer), SEBS (styrene)・ Styrene elastomers such as ethylene / butylene / styrene block copolymer), SEPS (styrene / ethylene / propylene / styrene block copolymer), SIS (styrene / isoprene / styrene copolymer), EEA (ethylene / acrylic acid) Ethyl copolymer), EMA (ethylene / methacrylic acid methyl) Copolymer), EAA (ethylene / acrylic acid copolymer), EMAA (ethylene / methyl methacrylate copolymer) and other α-olefins (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), ionomer, etc. These impact resistant materials can be used, and two or more types of these impact resistant materials can be used in combination. In addition, it is preferable to use these impact-resistant materials after being acid-modified with a dicarboxylic acid such as maleic acid or itaconic acid or an anhydride thereof in order to obtain a more excellent mechanical strength.

  The blending amount of the (D) impact resistant material is preferably 5 to 30% by weight, more preferably 10 to 20% by weight, based on the entire resin composition. In addition, when the component (D) is less than 5% by weight, the impact improving effect is not sufficient, which is not preferable. When the component (D) exceeds 30% by weight, the mechanical strength is deteriorated, which is not preferable.

Examples of the (E) inorganic filler used in the present invention include glass fiber, carbon fiber, fibrous inorganic material such as wollastonite and potassium titanate whisker, montmorillonite, talc, mica, calcium carbonate, silica, clay, kaolin Inorganic fillers such as glass powder and glass beads, organic fillers such as various organic or polymer powders, and the like, preferably glass fibers or talc, more preferably glass fibers.
The fibrous filler has a fiber diameter of 0.01 to 20 μm, preferably 0.03 to 15 μm, and a fiber cut length of 0.5 to 10 mm, preferably 0.7 to 5 mm.

The amount of (E) inorganic filler used in the present invention is 0.5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the entire resin composition. .
When it is less than 0.5% by weight, the mechanical strength of the polyamide resin is not sufficiently satisfied. If it is more than 50% by weight, the mechanical strength is sufficiently satisfied, but the moldability and surface condition are deteriorated, which is not preferable.

  The resin composition of the present invention can be used as it is as a material for various parts as it is, but as long as the purpose is not impaired, a heat resisting agent, weathering agent, crystal nucleating agent, crystallization accelerator, mold release agent, lubricant, antistatic agent Functionality-imparting agents such as colorants can be used.

  The method for producing the polyamide resin composition of the present invention is not particularly limited, but (A) polyamide resin, (B) flame retardant, (C) red phosphorus, (D) impact resistant material, and (E) inorganic A method in which the filler is blended in advance using a mixer such as a Henschel mixer, a tumbler, and a ribbon blender, and is charged into a hopper of a single screw or twin screw extruder such as a screw extruder, and melt kneading, or each of the above components Blend one or a part of them in advance, put them into the hopper of a single screw or twin screw extruder, melt in the extruder, and then charge the remaining components from the melting zone in the middle of the extruder. There are ways to do it.

  Moreover, there is no restriction | limiting in particular about the method of shape | molding a molded article from the polyamide resin composition of this invention, The polyamide resin composition is injection-molded using an injection molding machine, or press-molding using a press molding machine. Can do.

1. Component used (A) Polyamide resin,
A1: Polyamide 6 (1011FB manufactured by Ube Industries, Ltd.)
A2: Polyamide 6 (1015B manufactured by Ube Industries, Ltd.)
A3: Polyamide 66 (2020B manufactured by Ube Industries)
A4: Polyamide 6I / 6T (Grivory G21 manufactured by EMS)
(B) Flame retardant B: Exolit OP1311 (TP) (manufactured by Clariant)
(C) Red phosphorus C1: 30 wt% red phosphorus master PA6 resin (Hishiguard LP Master, Nippon Chemical Industry Co., Ltd.)
C2: 50 wt% red phosphorus master PA6 resin (Clariant Japan Co., Ltd. Exolit RP694)
(D) Impact resistant material D1: ethylene / α-olefin copolymer (Tafmer MC1307, Mitsui Chemicals, Inc.)
(E) Inorganic filler E1: Carbon fiber (TR06NEB3E manufactured by Mitsubishi Rayon Co., Ltd.)
E2: Glass fiber (ECS03T-249H manufactured by Nippon Electric Glass Co., Ltd.)
(F) Other flame retardant F1: Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd. KISUMA5E)

2. Production, processing and testing of flame retardant plastic molding materials Each component shown in Table 1 is mixed and then mixed at a temperature of 260 ° C to 300 ° C (when using PA66) or 240 ° C to 280 ° C (when using PA6). Homogenize in a shaft screw extruder (ZSK4ZSK40 manufactured by WERNER & PFLEIDERER). The homogenized polymer extrudate was drawn, cooled in a water bath and then pelletized.

After sufficiently drying, the obtained molding material is injected at a melting temperature of 280 ° C. to 300 ° C. (when PA66 is used) or 270 ° C. to 290 ° C. (when PA6 is used). Specimens were fabricated using 100D) and tested and rated for their flame retardancy using the UL94 test (Underwriters Laboratories).
[Tensile strength and elongation at break] Measured by a method in accordance with ASTM D638.
[Bending strength and flexural modulus] Measured by a method based on ASTM D790.
[Izod impact strength] Measured by a method based on ASTM D256.

  Table 1 shows the test results of adding an impact resistant material to PA and using the flame retardant (B) and red phosphorus in combination as Examples 1 to 5. Moreover, the comparative examples 1-2 when not using a flame retardant (B), the comparative example 3 when not using red phosphorus together, and the comparative example 4 when not containing an impact-resistant material are shown.

The materials of Examples 1 and 2 have a high flame retardant effect without greatly impairing mechanical properties such as strength and impact resistance compared to the flame retardant effect when the flame retardant formulation of Comparative Examples 1 and 2 is changed. You can see that it has been achieved.
The materials of Examples 3 to 4 have effects equivalent to those of Examples 1 and 2 even when the type of polyamide resin is changed, and are useful as non-halogen flame retardants containing no bromine or the like.

  Comparative Example 3 is a composition containing only the flame retardant (B) without adding red phosphorus, but the flame retardant effect of the thin molded article is low. The material of one of Examples 1 and 2 is a thin molded article. Sufficient flame retardant effect is obtained and useful.

Comparative Example 4 is a composition that does not contain an impact-resistant material, which provides a flame-retardant effect but has low impact resistance. The materials of one of Examples 1 and 2 are the same as when other flame retardants are used. It turns out that it has the above impact resistance.

Claims (4)

(A) polyamide resin,
(B) As component B1, (B1a) phosphinic acid salt represented by the following formula (I) and / or (B1b) diphosphinic acid salt represented by the following formula (II), and / or (B1a ) And (B1b), and as component B2, (B2a) the condensation product of melamine, or (B2b) the reaction product of melamine and phosphoric acid, or (B2c) the condensation of melamine A flame retardant comprising a reaction product of a product and phosphoric acid, or a mixture comprising at least two of (B2a) to (B2c),
(C) Red phosphorus,
A flame retardant resin composition comprising (D) an impact resistant material and (E) an inorganic filler.

[Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl, and R ³ is linear or branched C ₁ -C ₁₀ - _alkylene, C 6 _{-C 10} - _arylene, C 6 _{-C 10} - alkylarylene or _C 6 _{-C 10} - aryl alkylene, M is calcium ions, magnesium ions, aluminum ions and / or zinc ions Wherein m is 2 or 3, n is 1 or 3, and x is 1 or 2. ] 30 to 80% by weight of the (A) polyamide resin, 1 to 30% by weight of the B1 component and 1 to 30% by weight of the B2 component of the flame retardant, (C) 1 to 20% by weight of red phosphorus, (D The flame-retardant resin composition according to claim 1, comprising 5) to 30% by weight of impact-resistant material and 0.5 to 50% by weight of (E) inorganic filler. The flame retardant resin composition according to claim 1 or 2, wherein the (A) aliphatic polyamide resin is polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12 or polyamide 6/66. Stuff. The molded product formed by shape | molding the flame-retardant resin composition as described in any one of Claims 1-3.