JP2002275372A - Flame retardancy-enhanced polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardancy-enhanced polyamide resin composition having extremely high flame retardancy, generating no highly corrosive hydrogen halide gas on combustion, excellent in mechanical characteristics and tenacity and, moreover, hardly causing bleeding. SOLUTION: The flame retardancy-intensified polyamide resin composition comprises the following components, (a) 30-85 wt.% of a polyamide resin, (b) 5-40 wt.% of an adduct formed from melamine and phosphoric acid, (c) 5-50 wt.% of an inorganic filler and (d) 0.01-5 wt.% of a monoester derivative from a polyalkylene polyhydric alcohol and a 10-30C higher fatty acid, components (a) through (d) adding up to 100 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polyamide resin composition. In particular, the present invention relates to a flame-retardant polyamide resin composition suitably used for components such as connectors, breakers, and magnet switches in the electric and electronic fields, and electrical components in the automotive field. In particular, the present invention
The present invention relates to a reinforced flame-retardant polyamide resin composition which has extremely high flame retardancy, does not generate highly corrosive hydrogen halide gas during combustion, has excellent mechanical properties and toughness, and further has little bleed.

[0002]

2. Description of the Related Art Conventionally, polyamide resins have a high mechanical strength,
Because of its excellent heat resistance, automotive parts, machine parts,
Used in fields such as electric and electronic components. In particular, in electric and electronic parts applications, the required level of flame retardancy is increasingly higher, and a higher degree of flame retardancy is required than the self-extinguishing property inherent to polyamide resins.
Numerous studies have been made on the enhancement of the flame retardant level conforming to the UL94V-0 standard of Underwriters Laboratory,
Then, generally, a method of adding a halogen-based flame retardant or a triazine-based flame retardant is used.

For example, addition of a chlorine-substituted polycyclic compound to a polyamide resin (JP-A-48-29846) and addition of a bromine-based flame retardant such as decabromodiphenyl ether (JP-A-47-7134). , Addition of brominated polystyrene (JP-A-51-47044,
No. 175371), addition of brominated polyphenylene ether (Japanese Patent Application Laid-Open No. 54-116054), addition of a brominated crosslinked aromatic polymer (Japanese Patent Application Laid-Open No. 63-317552), brominated styrene-maleic anhydride. Addition of polymers (JP-A-3-168246) is known.
In particular, a composition in which these halogen-based flame retardants are blended with a polyamide resin reinforced with glass fiber or the like is used for electric and electronic parts, especially for printed laminates, and connected, because of its high flame retardancy and high rigidity. It has been widely used for connector applications. However, halogen-based flame retardants are suspected of generating corrosive hydrogen halide and smoke during combustion and emitting toxic substances, and the use of plastic products containing halogen-based flame retardants has been restricted due to these environmental problems. There is a movement to do. For this reason, halogen-free triazine-based flame retardants have attracted attention, and many studies have been made. For example, a technique using melamine as a flame retardant (Japanese Patent Publication No. 47-1714), a technique using cyanuric acid (Japanese Patent Application Laid-Open No. 50-105744), and a technique using melamine cyanurate (Japanese Patent Application Laid-open No. 53-31759) No.)
Is well known. The unreinforced polyamide resin composition obtained by these techniques has a high flame retardant level conforming to the UL94V-0 standard, but in a composition reinforced with an inorganic reinforcing material such as glass fiber to increase rigidity, Even when a large amount of a flame retardant is added, there is a problem that cotton ignition occurs at the time of combustion, which does not conform to the UL94V-0 standard.

[0004] On the other hand, halogen-free flame retardant technology using melamine phosphate, melamine pyrophosphate or melamine polyphosphate as an intumescent type flame retardant in a glass fiber reinforced polyamide resin (Japanese Patent Application Laid-Open No. 10-505875).
Publication), a flame retardant technology (WO98 / 45364) in which melamine polyphosphate is added to an inorganic reinforced polyamide resin and a char forming catalyst and / or a char forming agent is used in combination,
Flame retardant standard UL94V for molded products of 1/16 inch
It is known to satisfy the −0 standard. However, according to these techniques, UL94 is used for a thin molded product of 1/32 inch which is particularly required for a connector of an electric / electronic part.
In order to satisfy the V-0 standard, it is necessary to use a large amount of melamine phosphate-based flame retardants, and therefore, not only the mechanical properties of the glass fiber reinforced polyamide resin composition are significantly reduced, but also the electrical properties, especially It is inferior in the tracking resistance required for electric parts used in a high voltage environment, and is not always satisfactory as a molding material for electric / electronic parts.

As a technique for achieving a flame retardant standard of UL94V0 in a thin molded article of 1/32 inch, a technique in which melamine sulfate which is an intumescent type flame retardant is applied to a glass fiber reinforced semi-aromatic polyamide resin (Japanese Patent Laid-Open 2000-
Japanese Patent Application Laid-Open No. 119512) is disclosed, but also in this technique, it is necessary to add a large amount of a flame retardant to the amount of the polyamide resin component, and there is a problem similar to the above. Furthermore, the flame-retardant standard UL9 for 1/32 inch thin molded products
As a technique for imparting high tracking resistance while achieving 4V-0, a technique (WO 00/09606) of blending an alkaline earth metal salt in addition to a melamine phosphate composite flame retardant with an inorganic reinforced polyamide resin has also been proposed. I have. However, molded products obtained by this technology are brittle, for example, when applied to connectors with complex shapes, such as when the connector is chipped or cracked during handling or transport,
There was a problem that toughness was poor. Also, for example, if the molded product is 6
When left for a long time in a high-temperature and high-humidity environment such as 0 ° C. and 95% RH, there is a problem that a polyamide oligomer or a flame retardant precipitates on the surface of a molded product, that is, a so-called bleed-out phenomenon occurs. Was.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to have extremely high flame retardancy, no generation of highly corrosive hydrogen halide gas during combustion, and excellent mechanical properties and toughness. An object of the present invention is to provide a reinforced flame-retardant polyamide resin composition having less bleed.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have applied a specific monoester derivative to a system combining an inorganic filler, a phosphorus-based flame retardant, and a polyamide resin. At this time, they have found that the above object can be achieved, and based on this finding, have completed the present invention. That is, the present invention relates to (a) polyamide resin 30 to
85% by weight, (b) 5-40% by weight of an adduct formed from melamine and phosphoric acid, (c) 5-50% by weight of inorganic filler, (d) polyalkylene polyhydric alcohol and carbon number 10
~ 30 monoester derivatives with higher fatty acids 0.01 ~
The reinforced flame-retardant polyamide resin composition is composed of 5% by weight of each component, and the total amount of the above-mentioned (a) to (d) is 100% by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The polyamide resin (a) used in the present invention is not particularly limited. Examples thereof include ε-caprolactam, adipic acid, sebacic acid, dodecane diacid, isophthalic acid, terephthalic acid, hexamethylene diamine, tetramethylene diamine, and 2-methyl Pentamethylenediamine, 2,2
4-trimethylhexamethylenediamine, 2,4,4-
Trimethylhexamethylenediamine, metaxylylenediamine, bis (3-methyl-4aminocyclohexyl)
Homopolymers, copolymers, and mixtures thereof obtained by appropriately combining polyamide-forming monomers such as methane can be used. Specifically, polyamide 66, polyamide 6, polyamide 610, polyamide 612, polyamide 6I (polyhexamethylene isophthalamide), MXD (meta-xylylenediamine) 6 nylon, their copolyamides, and mixtures thereof have a high heat resistance. Is preferred. Further, a semi-aromatic polyamide resin containing polyamide 66 (polyhexamethylene adipamide) units and polyamide 6I (polyhexamethylene isophthalamide) units as main constituents, particularly a semi-aromatic resin containing 5 to 30% by weight of polyamide 6I units. Group III polyamide resins are more preferred because they exhibit a high degree of flame retardancy when combined with a melamine phosphate flame retardant. Specific examples of the semi-aromatic polyamide resin include 70 to 95% by weight of a polyamide 66 (polyhexamethylene adipamide) unit and 5 to 5% of a polyamide 6I (polyhexamethylene isophthalamide) unit.
A copolymer (polyamide 66 / 6I) with 30% by weight is preferred because it satisfies heat resistance, molded article appearance, molding processability, and electrical properties.
In particular, a copolymer of 10% to 30% by weight of a polyamide 6I unit is particularly preferable because it has flame retardancy and good releasability during molding in addition to the above-mentioned properties.

Also, polyamide 66 70-95% by weight
A mixed polyamide of 5 and 30% by weight of polyamide 6I (polyhexamethylene isophthalamide) has high heat resistance and is preferred for applications requiring solder resistance. Also, 60 to 89% by weight of a polyamide 66 unit, 5 to 30% by weight of a polyamide 6I unit, and 1 to 10% by weight of another aliphatic polyamide unit in which a part of the polyamide 66 unit is replaced by another aliphatic polyamide unit. Is excellent in molding fluidity. Examples of such a terpolymer include caproamide units (polyamide 6 units), undecamide units (polyamide 11 units), dodecamide units (polyamide 12 units), hexamethylene sebacamide units (polyamide 610 units), and hexamethylene dodecamide. Tertiary copolymer in which a part of polyamide 66 unit is substituted by a unit (polyamide 612 unit), for example (polyamide 66
/ 6I / 6), (Polyamide 66 / 6I / 11), (Polyamide 66 / 6I / 12), (Polyamide 66 / 6I)
/ 610) and (polyamide 66 / 6I / 612).

The object of the present invention can be achieved even with a mixed polyamide comprising 60 to 89% by weight of polyamide 66 units, 5 to 30% by weight of polyamide 6I units and 1 to 10% by weight of other aliphatic polyamide units. . Polyamide 6
In the case of a copolymer or a mixed polyamide in which the I unit exceeds 30% by weight, heat resistance, moldability and electrical properties may not always be sufficient.
In the case of a copolymer or a mixed polyamide of less than% by weight, it is necessary to add a large amount of a flame retardant to obtain a sufficient flame retardant level.

The copolymer of the present invention may be either a random copolymer or a block copolymer, and these copolymers may be made of other aromatic polyamide resins as long as the object of the present invention is not impaired. May be contained as a copolymer component. The mixed polyamide is a polyamide obtained by mixing polyamides composed of two or more components by a generally used method other than polymerization such as blending and melt kneading. The semi-aromatic polyamide resin of the present invention may have a molecular weight within a range in which it can be molded, and a polyamide resin having a sulfuric acid relative viscosity in the range of 1.5 to 3.5 shown in JIS K6810 may have a molding fluidity. Is particularly preferable because it can maintain good flame retardancy level.

The (b) adduct formed from melamine and phosphoric acid used in the present invention means a product obtained from a substantially equimolar reaction product of melamine and phosphoric acid units. Has no particular restrictions. Usually, melamine polyphosphate obtained by heating and condensing melamine phosphate under a nitrogen atmosphere can be exemplified. Here, as the phosphoric acid constituting the melamine phosphate, specifically, orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid,
Tetraphosphoric acid and the like can be mentioned, and melamine polyphosphate obtained by condensing an adduct with melamine using orthophosphoric acid or pyrophosphoric acid is particularly preferred because of its high effect as a flame retardant. In particular, the condensation degree n of the melamine polyphosphate is preferably 5 or more from the viewpoint of heat resistance. The melamine polyphosphate may be an addition salt of polyphosphoric acid and melamine. Examples of polyphosphoric acid that forms an addition salt with melamine include chain polyphosphoric acid and so-called condensed phosphoric acid and cyclic polymetaphosphoric acid. The degree of condensation n of these polyphosphoric acids is not particularly limited and is usually 3 to 50, but the degree of condensation n of the polyphosphoric acid used here is preferably 5 or more from the viewpoint of the heat resistance of the resulting melamine polyphosphate addition salt. Such a melamine polyphosphate addition salt is a mixture of melamine and polyphosphoric acid, for example, a water slurry, after mixing well to form a reaction product of both into fine particles, filtration, washing, the slurry,
A powder obtained by drying and, if necessary, calcining and pulverizing the obtained solid.

In terms of the mechanical strength and appearance of the molded product obtained by molding the composition of the present invention, it is preferable to use a powder obtained by pulverizing the melamine polyphosphate to a particle size of 100 μm or less, preferably 50 μm or less. good. The use of a powder having a particle size of 0.5 to 20 μm is particularly preferable because not only high flame retardancy is exhibited, but also the strength of a molded article is significantly increased. Also, melamine polyphosphate does not necessarily have to be completely pure,
Some unreacted melamine, phosphoric acid, or polyphosphoric acid may remain. It is particularly preferable that melamine polyphosphate contains 10 to 18% by weight of phosphorus atoms as a phosphorus atom because a phenomenon that a contaminant adheres to a molding die during molding is small.

[0014] Melamine polyphosphate acts as a flame retardant. However, compared to triazine flame retardants represented by melamine cyanurate, melamine polyphosphate has a high degree of difficulty when used in combination with an inorganic filler such as glass fiber. It exhibits a flame-retardant effect, and exhibits a further higher flame-retardant effect, especially when it is blended with a copolymer of polyamide 66 and polyamide 6I and / or a mixed polyamide. As the inorganic filler (c) used in the present invention, glass fiber, carbon fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc,
Fibrous, granular, plate-like, or needle-like inorganic reinforcing materials such as silica, calcium carbonate, kaolin, calcined kaolin, wollastonite, glass beads, glass flakes, and titanium oxide. These reinforcing materials may be used in combination of two or more. Particularly, glass fiber, wollastonite, talc, calcined kaolin and mica are preferably used. The glass fiber can be selected from long fiber type roving, short fiber type chopped strand, milled fiber and the like. It is preferable to use glass fibers that have been surface-treated for polyamide.

The (d) monoester derivative of a polyalkylene polyhydric alcohol and a higher fatty acid having 10 to 30 carbon atoms, which is used in the present invention, exhibits a function and effect as a toughness improver. As polyethylene glycol, polypropylene glycol,
Dihydric alcohols such as polybutylene glycol; trihydric alcohols such as sorbitan and glycerin; these polyhydric alcohols, lauric acid, myristic acid,
Monoester derivatives with higher fatty acids having 10 to 30 carbon atoms, such as palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melicic acid, oleic acid, and erucic acid. Ester derivatives include mono-, di- or triesters, but the above-mentioned mono-ester derivatives are particularly preferred because they have a large effect of improving toughness without lowering flame retardancy. When the carbon number of the higher fatty acid is less than 10, not only the toughness is not improved but also the bleed out is not suppressed. When the number of carbon atoms exceeds 30, the flame retardancy decreases.

Specific examples of the monoester derivative of a polyalkylene polyhydric alcohol and a higher fatty acid include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, propylene glycol monostearate,
Polyoxyethylene bisphenol A laurate ester, pentaerythritol monooleate, pentaerythritol monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monobehenate, polyoxyethylene sorbitan Monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Examples thereof include polyoxyethylene sorbitan monooleate, monoglyceride stearate, monoglyceride palmitate, monoglyceride oleate, monoglyceride behenate, and monoglyceride caprate. In particular, monoester derivatives such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate, which have a high effect on toughness without reducing flame retardancy and are easily available industrially Is particularly preferred.
The molecular weight of the ester derivative is 1,000 to 1,000.
20,000 is preferred for this. When the molecular weight is less than 1,000, not only the toughness is not improved but also bleed-out is not suppressed. When the molecular weight exceeds 20,000, the flame retardancy decreases.

In a preferred embodiment of the present invention, in the reinforced flame-retardant polyamide resin composition comprising the components (a), (b), (c) and (d), the ratio of the main component (a) of the polyamide resin is as follows: The range is 30 to 85% by weight.
If it is less than 30% by weight, moldability and mechanical properties are impaired, and if it exceeds 85% by weight, flame retardancy and rigidity may be reduced. (B) The proportion of the adduct formed from melamine and phosphoric acid is in the range of 5 to 40% by weight, preferably 10 to 35% by weight. If it is less than 5% by weight, the flame retardant effect is not sufficient,
If it exceeds 40% by weight, decomposition gas is generated during kneading,
Problems such as adhesion of contaminants to a molding die during molding process occur. In addition, it also causes a significant decrease in mechanical properties and a deterioration in the appearance of a molded product. (C) The proportion of the inorganic filler is 5 to 50% by weight, preferably 10 to 40% by weight. If the amount is less than 5% by weight, no manifestation of mechanical strength and rigidity is observed. unacceptable. In the present invention, an inorganic flame retardant can be further added within a range that does not adversely affect the mechanical properties and moldability. Preferred flame retardant aids are magnesium hydroxide,
Examples include aluminum hydroxide, zinc sulfide, iron oxide, boron oxide, and zinc borate. (D) Polyalkylene polyhydric alcohol and carbon number 10 to 3
0 of the ester derivative with the higher fatty acid is 0.01%
-5% by weight, preferably 0.03-3% by weight.
If it is less than 0.01% by weight, the toughness is not improved and 5% by weight
If the ratio exceeds, not only the flame retardancy deteriorates, but also problems such as generation of gas during molding are caused. The method for producing the reinforced flame-retardant polyamide resin composition of the present invention is not particularly limited, and a polyamide resin, an additive formed from melamine and phosphoric acid, an inorganic filler, a polyalkylene polyhydric alcohol and / or The fatty acid ester derivative is mixed with a conventional single-screw or twin-screw extruder or kneader such as a kneader to obtain the fatty acid ester derivative.
Any method can be used as long as it is a method of melting and kneading at a temperature of 00 to 350 ° C.

The reinforced flame-retardant polyamide resin composition of the present invention may contain other components such as a coloring agent such as a pigment and a dye, and a general heat stabilizer of the polyamide resin, as long as the object of the present invention is not impaired. Heat stabilizers (eg, a combination of copper iodide, copper acetate, and the like with potassium iodide and potassium bromide), organic heat stabilizers represented by hindered phenol-based oxidation deterioration inhibitors, and weather resistance improvers , A nucleating agent, a plasticizer, an additive such as an antistatic agent, and other resin polymers.
The composition of the present invention is molded into various molded products for electric, electronic, and automotive applications such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs, and switches by known methods such as injection molding, extrusion molding, and blow molding. You. The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The raw materials and measurement methods used in the examples and comparative examples are shown below.

[Raw Materials] (A) Polyamide resin (a-1): Polyamide 6 obtained in Polymerization Example 1 described below.
6 / 6I (85/15) copolymer (a-2): polyamide 6 obtained in Polymerization Example 2 described below
6 / 6I (80/20) copolymer (a-3): polyamide 6 obtained in Polymerization Example 3 described below
6 / 6I (65/35) copolymer (a-4): polyamide 66 manufactured by Asahi Kasei Kogyo Co., Ltd.
Brand name Leona 1300 (a-5): Polyamide 6 Ube Industries, Ltd.
Brand name SF1013A (B) Flame retardant (b-1): Melamine polyphosphate manufactured by Sanwa Chemical Co., Ltd. Brand name Apinon MPP-A (C) Inorganic filler (c-1): Glass fiber, Asahi Fiberglass Co., Ltd. ) Product name CS03JAFT756
(Average fiber diameter 10 μm) (D) Polyhydric alcohol ester derivative (d-1): polyethylene glycol monolaurate
Kao Corporation product name Emanon 1112 (d-2): polyethylene glycol monostearate Kao Corporation product name Emanone 3199 (d-3): polyethylene glycol distearate
Kao Corporation product name Emanone 3299 (d-4): pentaerythritol monostearate
Exopearl PE-MS (d-5): polyethylene glycol monocaprate (d-6): polyethylene glycol monolaccelate manufactured by Kao Corporation

[Measurement Method] (1) Thin-walled flame retardant UL94 (Under Writers Labo, USA)
ratifications Inc.). The thickness of the test piece was 1/16 inch
And 1/32 inch injection molding machine (Toshiba Machinery: I
(S50EP). (2) Relative viscosity of sulfuric acid The relative viscosity with 98% sulfuric acid was measured according to JIS K6810. (3) Mechanical properties Using an injection molding machine (TOSHIBA MACHINE: IS50EP),
A bending test piece (thickness: 3 mm) of STM D790 was formed, and a bending test was performed by a method in accordance with ASTM D790 to determine bending strength and flexural modulus. (4) Toughness A flat plate having a width of 130 mm, a length of 130 mm, and a thickness of 1 mm was formed by using an injection molding machine (manufactured by Toshiba Machine Co., IS150E). A test piece having a width of 13 mm and a length of 130 mm was cut out from the molded piece at a position 20 mm from the opposite side of the gate and perpendicular to the flow direction, and a bending test was performed by a method in accordance with ASTM D790. The amount of deflection was determined. (5) Bleeding property The molded product was visually observed for bleeding which had precipitated on the surface of the molded product after being left for 240 hours in a constant-temperature and constant-humidity bath adjusted to a temperature of 60 ° C. and a relative humidity of 95%. The degree of bleed was determined based on the following criteria. ：: No bleed is observed on the surface of the molded product. ×: Bleed products are observed on the molded product surface.

[Polymerization Example 1] 5 L of 2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.35 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.1 kg of adipic acid and 2.5 kg of pure water Into an autoclave and stirred well. After sufficient nitrogen replacement, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. At this time, the internal pressure becomes 1.76 MPa as a gauge pressure due to the natural pressure of the steam in the autoclave, but heating was continued while removing water outside the reaction system so that the pressure did not become 1.76 MPa or more. After another 2 hours, the internal temperature becomes 2
When the temperature reached 60 ° C., the heating was stopped, the valve of the autoclave was closed, and the mixture was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of the polymer was taken out and pulverized. The obtained pulverized polymer was put in a 10 L evaporator and subjected to solid-state polymerization at 200 ° C. for 10 hours under a nitrogen stream. The polyamide obtained by solid-state polymerization had a melting point of 245 ° C. and a sulfuric acid relative viscosity of 2.38.

[Polymerization Example 2] Starting from 2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.50 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.1 kg of adipic acid and 2.5 kg of pure water A polyamide was produced in the same manner as in Polymerization Example 1 except that the raw materials were used.
The obtained polyamide had a melting point of 239 ° C. and a relative viscosity of sulfuric acid of 2.
41. [Polymerization Example 3] 1.67 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.88 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.1 k of adipic acid
g, and 2.5 kg of pure water were used as starting materials to prepare a polyamide in the same manner as in Polymerization Example 1. The obtained polyamide had a melting point of 219 ° C. and a sulfuric acid relative viscosity of 2.45.

[0023]

Example 1 Polyamide resin a-1 was 48.5% by weight,
25.0% by weight of flame retardant b-1 and 2 of glass fiber c-1
Using a twin screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.), set the cylinder temperature to 240% by weight and the fatty acid ester derivative d-2 of the polyhydric alcohol to 1.5% by weight.
° C, screw rotation 100rpm, discharge rate 30kg / h
Under the conditions of r, polyamide resin a-1, flame retardant b-1,
The fatty acid ester derivative d-2 of the polyhydric alcohol was top-fed and the glass fiber c-1 was side-kneaded and kneaded, taken out in a strand shape, cooled, and granulated with a cutter to obtain a polyamide resin composition pellet. Various characteristics of the obtained pellets were examined by the above-mentioned measuring methods. Table 1 shows the results.

[0024]

Example 2 Pellets were obtained in the same manner as in Example 1 except that a-2 was used as the polyamide resin, and various characteristics were examined. Table 1 shows the results.

[0025]

Example 3 Pellets were obtained in the same manner as in Example 1 except that a-3 was used as the polyamide resin, and various characteristics were examined. Table 1 shows the results.

[0026]

Example 4 A pellet was obtained in the same manner as in Example 1 except that a-4 was used as the polyamide resin, and various characteristics were examined. Table 1 shows the results.

[0027]

Example 5 Pellets were obtained in the same manner as in Example 1 except that a-5 was used as the polyamide resin, and various characteristics were examined. Table 1 shows the results.

[0028]

Comparative Examples 1 and 2 Polyamide resin a-2, flame retardant b
-1, a pellet was obtained in the same manner as in Example 1 except that the mixing amount of the glass fiber c-1 was set to the ratio shown in Table 1, and various characteristics were examined. Table 1 shows the results. As can be seen from Examples 1 to 5 and Comparative Examples 1 and 2, only when a polyamide resin is combined with an adduct formed from a specific amount of melamine and phosphoric acid and a specific amount of a fatty acid ester derivative of a polyhydric alcohol, All properties such as thin-walled flame retardancy, mechanical properties, and toughness can be satisfied.

[0029]

Example 6: 48.5% by weight of polyamide resin a-2,
25.0% by weight of flame retardant b-1 and 2 of glass fiber c-1
Using a twin screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.), set the cylinder temperature to 240% by weight and the fatty acid ester derivative d-1 of polyhydric alcohol to 1.5% by weight.
° C, screw rotation 100rpm, discharge rate 30kg / h
Under the conditions of r, the polyamide resin a-2, the flame retardant b-1 and the fatty acid ester derivative d-1 of the polyhydric alcohol are top-fed, and the glass fiber c-1 is side-fed and kneaded, and is taken out into a strand. After cooling, the mixture was granulated with a cutter to obtain polyamide resin composition pellets. Various characteristics of the obtained pellets were examined by the above-mentioned measuring methods. Table 2 shows the results.

[0030]

Examples 7 and 8 Pellets were obtained in the same manner as in Example 6, except that the fatty acid ester derivatives d-3 and d-4 of the polyhydric alcohol were used instead of the fatty acid ester derivative d-1 of the polyhydric alcohol. And various characteristics were examined. Table 2 shows the results.

[0031]

Comparative Example 3 The same as Example 6 except that the blending amounts of the polyamide resin a-2, the flame retardant b-1 and the glass fiber c-1 were as shown in Table 2 with the fatty acid ester derivative of the polyhydric alcohol being 0. To obtain pellets, and various characteristics were examined. The result is set to 2.

[0032]

Comparative Example 4 Example 6 was repeated except that the blending amounts of the polyamide resin a-2, the flame retardant b-1, the glass fiber c-1, and the fatty acid ester derivative d-3 of the polyhydric alcohol were as shown in Table 2.
A pellet was obtained in the same manner as described above, and various characteristics were examined. Table 2 shows the results.

[0033]

Comparative Examples 5 and 6 Pellets were obtained in the same manner as in Example 6 except that d-5 and d-6 were used as fatty acid ester derivatives of polyhydric alcohol and the blending amounts were as shown in Table 2. The characteristics were investigated. Table 2 shows the results.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

The composition of the present invention has extremely high flame retardancy even in a thin molded article, does not generate highly corrosive hydrogen halide gas during combustion, and has excellent mechanical properties and toughness.
It is a molding material that also has a brie dress,
It can be used for applications such as electronic parts and automobile parts.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 7/14 C08K 7/14 F term (reference) 4J002 CL001 CL011 CL021 CL031 DA017 DE097 DE117 DE187 DE237 DG057 DJ007 DJ017 DJ037 DJ047 DJ057 DK007 DL007 EH048 EH058 EW046 FA047 FD017 FD136 FD208 GQ00

Claims (9)

[Claims] 1. An adduct 5 formed from (a) 30 to 85% by weight of a polyamide resin and (b) melamine and phosphoric acid.
(C) 5 to 50% by weight of an inorganic filler, and (d) polyalkylene polyhydric alcohol and 10 to 10 carbon atoms.
Monoester derivative with higher fatty acid of 30 to 0.01 to 5
(A) to (d).
A reinforced flame-retardant polyamide resin composition having a total amount of 100% by weight. 2. The method according to claim 1, wherein (a) the polyamide resin is polyamide 6;
6, polyamide 6, polyamide 610, polyamide 61
2. The reinforced flame-retardant polyamide resin composition according to claim 1, comprising polyamide 6I (polyhexamethylene isophthalamide), MXD6 nylon, and at least one selected from these copolyamides. . 3. The method according to claim 1, wherein the polyamide resin comprises:
The reinforced flame-retardant polyamide resin composition according to claim 1, comprising at least one selected from (4). (1) 70 to 95% by weight of polyamide 66 units and polyamide 6I (polyhexamethylene isophthalamide) units 5
(2) 60 to 89% by weight of a polyamide 66 unit, 5 to 30% by weight of a polyamide 6I unit and 1 to 10% by weight of an aliphatic polyamide unit (however, excluding the polyamide 66 unit). (3) Mixed polyamide of 70 to 95% by weight of polyamide 66 and 5 to 30% by weight of polyamide 6I (4) 60 to 89% by weight of polyamide 66 and 5 to 30% by weight of polyamide 6I and aliphatic Polyamide mixed with 1 to 10% by weight of polyamide units (excluding 66 units of polyamide). 4. The reinforced flame retardant according to claim 1, wherein the polyamide resin has a relative viscosity of sulfuric acid (measured according to JIS K6810) of 1.5 to 3.5. Polyamide resin composition. 5. An ester derivative of (d) a polyalkylene polyhydric alcohol and a higher fatty acid having 10 to 30 carbon atoms,
5. A monoester derivative of a higher fatty acid of at least one polyhydric alcohol selected from polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate. Reinforced flame retardant polyamide resin composition. (B) the adduct formed from melamine and phosphoric acid is at least one phosphorus flame retardant selected from melamine phosphate, melamine pyrophosphate and melamine polyphosphate. The reinforced flame-retardant polyamide resin composition according to claim 1. 7. The method according to claim 1, wherein the phosphorus-based flame retardant has a phosphorus atom of 10 to 10.
The reinforced flame-retardant polyamide resin composition according to claim 6, wherein the composition contains 18% by weight. 8. The phosphorus-based flame retardant having an average particle size of 0.5 to 2
The reinforced flame-retardant polyamide resin composition according to claim 6, wherein the thickness is 0 µm. 9. The method according to claim 1, wherein (c) the inorganic filler is at least one kind of reinforcing material selected from glass fiber, wollastonite, talc, calcined kaolin, and mica. The reinforced flame-retardant polyamide resin composition according to any one of the above.