JP2003292774A - Heat-resistant flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a heat-resistant polyamide flame-retardant resin composition having excellent flame retardance, generating no hydrogen halide in incineration and having excellent mechanical properties, toughness and resistance to heat aging. <P>SOLUTION: This heat-resistant flame-retardant resin composition comprises ingredients of (a) 30-85 wt.% polyamide resin, (b) 5-40 wt.% adduct comprising melamine and phosphoric acid, (c) 5-50 wt.% inorganic filer, (d) 0.01-5 wt.% monoester derivative between a polyalkylene polyhydric alcohol and a 10-30C higher fatty acid, (e) 0.0003-0.1 wt.% copper compound and (f) 0.01-0.5 wt.% organic heat stabilizer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polyamide composition. In particular, the present invention relates to a flame-retardant polyamide resin composition which is suitably used as a material for parts such as connectors in electric and electronic fields, breakers, magnet switches and the like, and electric components in the field of automobiles. In particular, the present invention has extremely high thin-wall flame retardancy, does not generate highly corrosive hydrogen halide gas during combustion, and has excellent mechanical properties and toughness, and also has excellent heat aging resistance. It relates to a flame-retardant resin composition.

[0002]

2. Description of the Related Art Conventionally, polyamide resin has a high mechanical strength,
Since it has excellent heat resistance, it can be used for automobile parts, machine parts,
It is used in fields such as electrical and electronic parts. In particular, in electrical and electronic parts applications, the required level of flame retardancy is increasing, and higher flame retardancy than the self-extinguishing properties inherent in polyamide resins is required.
Many studies have been conducted to improve the flame retardancy level that complies with UL94V-0 standard of Underwriters Laboratory.
In general, a method of adding a halogen-based flame retardant or a triazine-based flame retardant is used for them.

For example, addition of a chlorine-substituted polycyclic compound to a polyamide resin (JP-A-48-29846) or a brominated flame retardant such as decabromodiphenyl ether (JP-A-47-7134). Addition of brominated polystyrene (JP-A-51-47044, JP-A-4)
No. 175371), addition of brominated polyphenylene ether (JP-A No. 54-116054), addition of brominated cross-linked aromatic polymer (JP-A No. 63-317552), brominated styrene-maleic anhydride Addition of coalescence (Japanese Patent Laid-Open No. 3-168246) and the like are known.
In particular, compositions containing these halogen-based flame retardants in polyamide resin reinforced with glass fibers, etc. are used for electrical and electronic parts, especially mounted on printed laminates or connected due to their high flame retardancy and high rigidity. It has been widely used for connectors.

However, it is suspected that halogen-based flame retardants generate corrosive hydrogen halide and smoke during combustion, or emit toxic substances. Due to these environmental problems, plastic products containing halogen-based flame retardants have been suspected. There are moves to regulate the use. For this reason, halogen-free triazine flame retardants have attracted attention and many studies have been made. For example, a technique of using melamine as a flame retardant (Japanese Patent Publication No. 47-1714), a technique of using cyanuric acid (Japanese Patent Laid-Open No. 50-105744), and a technique of using melamine cyanurate (Japanese Patent Laid-Open No. 53-31759). Issue)
Is well known. Although the non-reinforced polyamide resin composition obtained by these techniques has a high flame retardance level that complies with UL94V-0 standard, it is reinforced with an inorganic reinforcing material such as glass fiber to increase the rigidity. Even when a large amount of flame retardant is blended, there is a problem of non-compliance with UL94V-0 standard due to the phenomenon of cotton ignition during combustion.

On the other hand, a halogen-free flame-retardant technique using melamine phosphate, melamine pyrophosphate or melamine polyphosphate, which are intimate flame retardants, in a glass fiber reinforced polyamide resin (Japanese Patent Publication No. 10-505875). A flame-retardant technique (WO98 / 45364) has been proposed in which melamine polyphosphate is added to an inorganic-reinforced polyamide resin and a char-forming catalyst and / or a char-forming agent are used in combination.
Flame retardant standard UL94V- for molded products of / 16 inch
It is known to satisfy the 0 standard.

However, in these technologies, 1/32 inch, which is particularly required for the use of connectors for electric / electronic parts
In order to satisfy the UL94V-0 standard in the thin-walled molded product, it is necessary to use a large amount of melamine phosphate flame retardant,
Therefore, not only the mechanical properties of the glass fiber reinforced polyamide resin composition are significantly deteriorated, but also the electrical properties, particularly the tracking resistance required for electric parts used under a high voltage environment, are poor. Further, if the molding is carried out at a high molding temperature for a long period of time, mold corrosion is likely to occur, which is not always satisfactory as a molding material for electric / electronic parts.

Further, as a technique for achieving the flame retardancy standard UL94V0 for 1/32 inch thin-walled molded products, a technique in which an intimate flame retardant melamine sulfate is applied to a glass fiber reinforced semi-aromatic polyamide resin (JP 2000
No. 119512), however, this technique also requires the addition of a large amount of a flame retardant with respect to the amount of polyamide resin component, and has the same problem as described above. Furthermore, the flame-retardant standard UL for 1/32 inch thin molded products
As a technique of imparting high tracking resistance while achieving 94V-0, a technique (WO00 / 09606) of adding an alkaline earth metal salt to an inorganic-reinforced polyamide resin in addition to a melamine phosphate composite flame retardant is also proposed. There is. However, the molded product obtained by this technique is brittle, and when applied to a connector having a complicated shape, for example, there was a problem that the toughness was poor such that the connector was chipped during handling or transportation, or cracking occurred. . Further, when the molded piece is left at a high temperature for a long period of time, the mechanical properties are largely deteriorated, and the surface of the molded piece is remarkably discolored, so that the heat aging property is not satisfactory.

[0008]

DISCLOSURE OF THE INVENTION The object of the present invention is that the flame retardance is extremely high, no highly corrosive hydrogen halide gas is generated during combustion, and excellent mechanical properties and toughness are maintained. Another object of the present invention is to provide a heat resistant flame retardant resin composition having excellent heat aging resistance.

[0009]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have found that in a system in which an inorganic filler, a phosphorus-based flame retardant and a polyamide resin are combined, a specific monoester derivative and a specific copper When applying the compound and a specific organic heat stabilizer, it was found that the above objects can be achieved,
The present invention has been completed based on this finding. That is, the present invention provides (a) 30 to 85% by weight of a polyamide resin, and (b) an adduct 5 formed from melamine and phosphoric acid.
˜40% by weight, (c) inorganic filler 5 to 50% by weight,
(D) Polyalkylene polyhydric alcohol and 10 to 3 carbon atoms
0.01 to 5% by weight of a monoester derivative with a higher fatty acid of 0, (e) a copper compound 0.0003 to 0.1% by weight, and (f) an organic heat stabilizer 0.01 to 0.5% by weight And a heat-resistant flame-retardant resin composition comprising the above components (a) to (f) in a total amount of 100% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The (a) polyamide resin used in the present invention is not particularly limited, and examples thereof include ε-caprolactam, adipic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, hexamethylenediamine, tetramethylenediamine 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
(Metaxylylenediamine) 6 nylon, copolyamides thereof, and mixtures thereof are preferable in terms of heat resistance. Also, a semi-aromatic polyamide resin containing polyamide 66 (polyhexamethylene adipamide) units and polyamide 6I (polyhexamethylene isophthalamide) units as main constituents, especially semi-aromatic containing 5 to 30% by weight of polyamide 6I units. Group polyamide resins are more preferable because they exhibit high flame retardancy when combined with a melamine phosphate flame retardant.

As the semi-aromatic polyamide resin, specifically, a mixture of 70 to 95% by weight of polyamide 66 (polyhexamethylene adipamide) unit and 5 to 30% by weight of polyamide 6I (polyhexamethylene isophthalamide) unit is used. A polymer (polyamide 66 / 6I) is preferable because it satisfies heat resistance, molded product appearance, molding processability, and electrical characteristics.
In particular, a copolymer of 70 to 90% by weight of polyamide 66 unit and 10 to 30% by weight of polyamide 6I unit is particularly preferable because it has flame retardancy and good mold releasability during molding in addition to the above characteristics.

Polyamide 66 70 to 95% by weight
Polyamide 6I (polyhexamethyleneisophthalamide) mixed polyamide of 5 to 30% by weight has high heat resistance and is preferable for applications requiring solder resistance. Also,
Polyamide 66 units 60 to 89% by weight, in which some of the polyamide 66 units are replaced with other aliphatic polyamide units,
A terpolymer composed of 5 to 30% by weight of a polyamide 6I unit and 1 to 10% by weight of another aliphatic polyamide unit has excellent molding fluidity. Examples of such terpolymers include caproamide units (polyamide 6 units), undecaamide units (polyamide 11 units), dodecaamide units (polyamide 12 units), hexamethylene sebacamide units (polyamide 610 units), hexamethylene dodecamide. A terpolymer in which a part of the polyamide 66 unit is replaced with a unit (polyamide 612 unit), for example (polyamide 6
6 / 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 unit, 5 to 30% by weight of polyamide 6I unit, and 1 to 10% by weight of other aliphatic polyamide unit. . Polyamide 6
In the case of a copolymer or mixed polyamide having an I unit of more than 30% by weight, heat resistance, moldability and electrical properties may not always be sufficient, while a polyamide 6I unit has 5 units.
In the case of less than wt% copolymer or mixed polyamide, it is necessary to add a large amount of 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 other aromatic polyamide resins as long as the object of the present invention is not impaired. May be included as a copolymerization component. The mixed polyamide is a polyamide obtained by mixing a polyamide composed of two or more components by a generally used method other than polymerization such as blending and melt kneading. The molecular weight of the semi-aromatic polyamide resin of the present invention may be in a moldable range, and the polyamide resin having a sulfuric acid relative viscosity of 1.5 to 3.5 according to JIS K6810 has a molding fluidity. Is preferable and a high flame retardancy level can be maintained, which is particularly preferable.

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. There are no particular restrictions. Usually, a melamine polyphosphate obtained by heat-condensing melamine phosphate under a nitrogen atmosphere can be mentioned. As the phosphoric acid constituting the melamine phosphate, specifically, orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid,
Examples thereof include tetraphosphoric acid, and melamine polyphosphate, which is obtained by condensing an adduct of orthophosphoric acid and pyrophosphoric acid with melamine, is particularly preferable because it has a high effect as a flame retardant.

The melamine polyphosphate may be an addition salt of polyphosphoric acid and melamine, and as the polyphosphoric acid forming the addition salt with melamine, a chain polyphosphoric acid called a so-called condensed phosphoric acid and a cyclic polymetaphosphoric acid may be used. Can be mentioned. The condensation degree n of these polyphosphoric acids is not particularly limited and is usually 3 to 50, but the condensation degree n of the polyphosphoric acid used here is preferably 5 or more from the viewpoint of heat resistance of the resulting melamine addition salt of polyphosphoric acid. Such a melamine polyphosphate addition salt is a mixture of melamine and polyphosphoric acid, for example, made into a water slurry, and mixed well to form a reaction product of the both in the form of fine particles, and then the slurry is filtered, washed and dried. Further, it is a powder obtained by further calcination if necessary and pulverizing the obtained solid material.

From the viewpoint of the mechanical strength of the molded product obtained by molding the composition of the present invention and the appearance of the molded product, melamine polyphosphate having a particle size of 100 μm or less, preferably 50 μm or less is used. good. Use of a powder of 0.5 to 20 μm is particularly preferable because not only high flame retardancy is exhibited, but also the strength of the molded product is significantly increased. Also, melamine polyphosphate does not necessarily have to be completely pure,
Some unreacted melamine, phosphoric acid, or polyphosphoric acid may remain. Those containing 10 to 18% by weight as a phosphorus atom in melamine polyphosphate are particularly preferable because there is little phenomenon that contaminants adhere to the molding die during molding. Melamine polyphosphate acts as a flame retardant, but compared to triazine flame retardants represented by melamine cyanurate, when used in combination with an inorganic filler such as glass fiber, a high flame retarding effect. In particular, when blended with a copolymer of polyamide 66 and polyamide 6I and / or a mixed polyamide, a higher flame retarding effect is exhibited.

As the inorganic filler (c) used in the present invention, glass fiber, carbon fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, Examples thereof include fibrous, granular, plate-shaped, or needle-shaped inorganic reinforcing materials such as silica, calcium carbonate, kaolin, calcined kaolin, wollastonite, glass beads, glass flakes, and titanium oxide. You may use these reinforcing materials in combination of 2 or more types. In particular, 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. As the glass fiber, it is preferable to use a surface-treated glass fiber.

The monoester derivative (d) of the polyalkylene polyhydric alcohol and the higher fatty acid having 10 to 30 carbon atoms, which is used in the present invention, has a function and effect as a toughness improver. As polyethylene glycol, polypropylene glycol,
Dihydric alcohols such as polybutylene glycol, and trihydric alcohols such as sorbitan and glycerin. These polyhydric alcohols, lauric acid, myristic acid,
It is a monoester derivative with a higher fatty acid having 10 to 30 carbon atoms such as palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, oleic acid, and erucic acid.

Examples of the ester derivative include mono-, di-, and triesters.
It is particularly preferable because the effect of improving the toughness is large without lowering the flame retardancy. When the carbon number of the higher fatty acid is less than 10, not only does the toughness not be improved, but also bleed out is not suppressed. If the carbon number exceeds 30, the flame retardancy will decrease. Specific examples of the monoester derivative of polyalkylene polyhydric alcohol and higher fatty acid include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, propylene glycol monostearate, and polyoxyethylene bisphenol A. Examples include lauric acid ester, pentaerythritol monooleate, pentaerythritol monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, and sorbitan monobehenate.

Further, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, behenin. Examples thereof include acid monoglyceride and capric acid monoglyceride. In particular, without reducing flame retardancy,
Particularly preferred are monoester derivatives such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monoeleate, which have a high effect on improving the toughness and are industrially easily available. The molecular weight of the above ester derivative is 1,0
The range of 00 to 20,000 is preferable. Molecular weight 1,000
When it is less than 1, not only toughness is not improved, but also bleed out is not suppressed. When the molecular weight exceeds 20,000, the flame retardancy decreases.

The (e) copper compound used in the present invention is
With the effect of improving the heat aging property of the polyamide resin composition, particularly, suppressing the deterioration of mechanical properties when the molded piece is left at high temperature for a long time, and suppressing the discoloration of the surface of the molded piece. is there. Examples of the copper compound include salts of inorganic acids such as copper chloride, copper bromide, copper iodide, copper sulfate, copper nitrate and copper phosphate, or copper acetate, copper stearate, copper myristate, copper naphthenate, palmitic acid. Examples thereof include organic acid salts such as copper, and these may be used in combination of two or more kinds.

As the organic heat stabilizer (f) used in the present invention, the effect of improving the heat aging property of the polyamide resin composition is suppressed, and particularly the deterioration of mechanical properties when the molded piece is left at high temperature for a long period of time is suppressed. In addition, it has an effect of suppressing discoloration of the surface of the molded piece, and it works more effectively when used in combination with a copper compound. Examples of the organic heat stabilizer include a phenol stabilizer, a phosphorus stabilizer, and an amine stabilizer, and two or more kinds of these may be used in combination.

Specifically, as the phenolic stabilizer,
Hindered phenol compounds can be preferably used. For example, triethylene glycol-bis [3-
(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 4,4′-butylidene bis (3-
Methyl-6-t-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,
5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

Further, 2,2-thiobis (4-methyl-6)
-1-butylphenol), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxynamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphas Phonate-diethyl ester,
1,3,5-Trimethyl-2,4,6-tris (3,5
-Di-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonic acid ethyl calcium, tris- (3,5-di-
t-Butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-t-
Butylphenol), 2,2'-methylene-bis- (4
-Ethyl-6-t-butylphenol) and 4,4'-thiobis- (3-methyl-6-t-butylphenol).

Further, octylated diphenylamine, 2,
4-bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, 4,4'-butylidene bis (3-methyl-6-t-butylphenol, 3,9-bis [1,1-dimethyl-2- [β- (3
-T-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene.

Also, bis [3,3'-bis- (4'-hydroxy-3'-T-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di- t-Butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3
H, 5H) trione, d-α-tocopherol and the like can be exemplified. As the phosphorus-based stabilizer, an organic phosphorus-based compound can be preferably used. For example, tetrakis (2,4-di-t-butylphenyl) -4,4
'-Biphenylene phosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4
6-di-t-butylphenyl) octyl phosphite,
Triphenyl phosphite, tris (2,4-di-t-
Butylphenyl) phosphite, diphenylisodecylphosphite, and phenyldiisodecylphosphite.

Further, 4,4-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetrayl Bis (2,6-di-t-butyl-4-methylphenyl) phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 1
0- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9 Examples thereof include -oxa-10-phosphaphenanthrene.

As the amine stabilizer, hindered amine compounds can be preferably used. For example,
Dimethyl succinate-1- (2-hydroxyethyl) -4
-Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly-[[6- (1,1,3,3-tetramethylbutyl) imino 1,3,5-triazine-2,
4-diyl] [2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [[2,2,5,6
-Tetramethyl-4-piperidyl) imino] 2- (3,3
5-di-t-butyl-4-hydroxybenzyl) -2-
It is bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butylmalonate.

Further, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis-2,2,6,6-tetramethyl-4- Piperidyl-sebacate, bis (1,2,
2,6,6-Pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-)
Piperidyl) sebacate, 1- [2- [3- (3.5-
Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-t-butyl-hydroxyphenyl) propionyloxy] 2,2
Examples thereof include 6,6-tetramethylpiperidine and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

The method of adding (d) the copper compound and (e) the organic heat stabilizer is not particularly limited. A method of adding the polyamide resin at the time of polymerization, a method of melt-kneading the polyamide resin and the flame retardant, other additives and a copper compound using a kneader such as a conventional single-screw or twin-screw extruder or a kneader may be used. .

In a preferred embodiment of the present invention, the components (a), (b), (c), (d), (e) and (f).
In the flame-retardant polyamide resin composition, the proportion of the main component (a) polyamide resin is 30 to 85% by weight.
Is the range. If it is less than 30% by weight, moldability and mechanical properties are impaired, and if it exceeds 85% by weight, flame retardancy and deterioration of rigidity may occur.

(B) The proportion of the adduct formed from melamine and phosphoric acid is 5 to 40% by weight, preferably 10 to 3
It is in the range of 5% by weight. If it is less than 5% by weight, the flame retardant effect is not sufficient, and if it exceeds 40% by weight, problems such as generation of decomposition gas during kneading and adhesion of pollutants to the molding die during molding process occur. In addition, it may cause a remarkable deterioration of mechanical properties and a deterioration of the appearance of the molded product. The proportion of the inorganic filler (c) is 5 to 50% by weight, preferably 10 to 40% by weight. If it is less than 5% by weight, no manifestation of mechanical strength and rigidity is observed, and if it exceeds 50% by weight, not only the molding processability during extrusion and injection molding is significantly lowered, but also the quantitative physical property improving effect is obtained. unacceptable.

(D) The proportion of the ester derivative of the polyalkylene polyhydric alcohol and the higher fatty acid having 10 to 30 carbon atoms is 0.01 to 5% by weight, preferably 0.03 to 3% by weight. If it is less than 0.01% by weight, the toughness is not improved, and if it exceeds 5% by weight, not only the flame retardancy is deteriorated, but also a problem such as generation of gas during molding occurs. The proportion of the (e) copper compound is in the range of 0.0003 to 0.1% by weight, preferably 0.0005 to 0.08% by weight. If it is less than 0.0003% by weight, the effect of improving heat aging is not recognized, and if it exceeds 0.08% by weight, the flame retardancy deteriorates. The proportion of the organic heat stabilizer (f) is 0.01 to 0.5% by weight, preferably 0.02 to 0.3% by weight. 0.0
If it is less than 1% by weight, the heat aging improving effect is not recognized, and if it exceeds 0.5% by weight, the flame retardancy deteriorates.

In the present invention, it is also possible to add an inorganic flame-retardant aid within a range that does not adversely affect mechanical properties and molding processability. Preferred flame retardant aids include magnesium hydroxide, aluminum hydroxide, zinc sulfide, iron oxide, boron oxide, zinc borate and the like. The method for producing the heat-resistant polyamide flame-retardant resin composition of the present invention is not particularly limited, and a polyamide resin, a flame retardant, an inorganic filler, and a copper compound are commonly used in single-screw or twin-screw extruders and kneaders. Any method such as melt kneading at a temperature of 200 to 350 ° C. using a kneader may be used. The heat-resistant polyamide flame-retardant resin composition of the present invention, to the extent that the object of the present invention is not impaired,
Other components, for example, colorants such as pigments and dyes, additives such as weather resistance improvers, nucleating agents, plasticizers and antistatic agents, and other resin polymers can be added.

The compositions of the present invention are injection molded, extruded,
By known methods such as blow molding, connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs,
Molded into various molded products for electrical, electronic, and automotive applications such as switches.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in more detail by the following examples, but the present invention is not limited thereto. The raw materials and measuring methods used in Examples and Comparative Examples are shown below. [Raw materials] (A) Polyamide resin (a-1): Polyamide 6 obtained in Polymerization Example 1 described later
6 / 6I (85/15) copolymer (a-2): Polyamide 6 obtained in Polymerization Example 2 described later
6 / 6I (80/20) Copolymer (a-3): Polyamide 6 obtained in Polymerization Example 3 described later
6 / 6I (65/35) copolymer (a-4): Polyamide 66 manufactured by Asahi Kasei Kogyo Co., Ltd.
Product name Leona 1300 (a-5): Polyamide 6 Ube Industries, Ltd.
Product name SF1013A

[0039]   (B) Flame retardant   (B-1): Melamine polyphosphate manufactured by Sanwa Chemical Co., Ltd. Product name Apino MPP-A   (B-2): Melamine phosphate manufactured by Sanwa Chemical Co., Ltd. Product name Apino P-7202   (C) Inorganic filler   (C-1): Glass fiber, product name CS03J manufactured by Asahi Fiber Glass Co., Ltd. A FT756 (Average fiber diameter 10 μm)   (D) Polyhydric alcohol ester derivative   (D-1): Polyethylene glycol monostearate manufactured by Kao Corporation               Product name Emanone 3199   (E) Copper compound   (E-1): Copper acetate First grade reagent manufactured by Katayama Chemical Co., Ltd.   (E-2): Copper iodide Katayama Chemical Co., Ltd. first-grade reagent

[0040]   (F) Organic heat stabilizer   (F-1): Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl) L-4-hydroxyphenyl) propionate]                 Product name IRGANOX1010   (F-2): N, N'-hexamethylenebis (3,5-di-t-butyl-4) -Hydroxynamamide)                 Product name IRGANOX 1098   (F-3): cyclic neopentanetetraylbis (2,6-di-t-bu) Chill-4-methylphenyl) phosphite manufactured by Asahi Denka Co., Ltd.                 Product name ADEKA STAB PEP-36   (F-4): 1- [2- [3- (3.5-di-t-butyl-4-hydroxyphenyl) Phenyl) propionyloxy] ethyl] -4- [3- (3,5-t-butyl-hi) Droxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperi gin                 Product name Sanor LS-2626

[Measurement Method] (1) Thin Flame Retardant UL94 (Under Writers Labo, USA)
It was measured in accordance with the method of the standards defined by the ratories Inc.). The thickness of the test piece is 1/32 inch
Was obtained by molding using an injection molding machine (PS40E manufactured by Nissei Plastic Industry Co., Ltd.). (2) Sulfuric acid relative viscosity The relative viscosity in 98% sulfuric acid was measured according to JIS K6810. (3) Mechanical characteristics Using an injection molding machine (TOSHIBA MACHINE: IS50EP),
A bending test piece (thickness: 3 mm) of STM D790 was molded, and a bending test was carried out by a method based on ASTM D790 to obtain bending strength and bending elastic modulus.

(4) Using a toughness injection molding machine (TOSHIBA MACHINE: IS150E), a flat plate having a width of 130 mm, a length of 130 mm and a thickness of 1 mm was molded. A test piece having a width of 13 mm and a length of 130 mm was cut out from this molded piece at a position 20 mm from the opposite gate side at right angles to the flow direction, and a bending test was carried out by a method according to ASTM D790, and bending was performed at a span length of 25 mm. The amount of deflection was calculated.

(5) ASTM D790 bending test piece (thickness: 3 mm) molded by using a heat aging injection molding machine (manufactured by Toshiba Machine: IS50EP)
Was left in an air oven at 120 ° C. for 1000 hours, taken out, cooled, and then subjected to a bending test by a method in accordance with ASTM D790 to obtain bending strength. The obtained value was divided by the value before heat aging to obtain the retention rate.

Polymerization Example 1 5.00 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 5 L The mixture was placed in the autoclave of and well stirred. After sufficiently substituting with nitrogen, the temperature was raised from room temperature to 220 ° C. over about 1 hour while stirring. At this time, the internal pressure was 1.76 MPa as a gauge pressure due to the natural pressure of water vapor in the autoclave, but heating was continued while removing water outside the reaction system so that the pressure did not exceed 1.76 MPa. After 2 hours, the internal temperature is 2
When the temperature reached 60 ° C, the heating was stopped, the valve of the autoclave was closed, and the temperature was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of polymer was taken out and pulverized. The obtained pulverized polymer was placed in a 10 L evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The polyamide obtained by solid phase 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 prepared in the same manner as in Polymerization Example 1 except that it was used as a raw material.
The obtained polyamide has a melting point of 239 ° C. and a relative viscosity of sulfuric acid of 2.
It was 41.

Polymerization Example 3 Starting with 1.67 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.88 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 prepared in the same manner as in Polymerization Example 1 except that it was used as a raw material.
The obtained polyamide has a melting point of 219 ° C. and a relative viscosity of sulfuric acid of 2.
It was 45.

[0047]

Example 1 48.4% by weight of polyamide resin a-1
25.0% by weight of flame retardant b-1 and 2 of glass fiber c-1
5.0 wt%, fatty acid ester derivative d-1 of polyhydric alcohol 1.5 wt%, copper compound e-2 0.029 wt%, organic heat stabilizer f-2 0.1 wt% Using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.), the cylinder set temperature is 240 ° C., the screw rotation is 100 rpm,
Under the condition that the discharge rate is 30 kg / hr, the polyamide resin a-
1, flame retardant b-1, polyhydric alcohol fatty acid ester derivative d-1, copper compound e-2 and organic heat stabilizer f-
2 was top-fed and the glass fiber c-1 was side-fed and kneaded, taken out in a strand form, cooled, and granulated with a cutter to obtain a polyamide resin composition pellet. Various characteristics of the obtained pellet were examined by the above-described measuring method. The results are shown in Table 1.

[0048]

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 properties were examined. The results are shown in Table 1.

[0049]

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 properties were examined. The results are shown in Table 1.

[0050]

Example 4 Pellets were obtained in the same manner as in Example 1 except that a-4 was used as the polyamide resin, and various properties were examined. The results are shown in Table 1.

[0051]

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 properties were examined. The results are shown in Table 1.

[0052]

Example 6 Pellets were obtained in the same manner as in Example 1 except that a-2 and a-5 were used as the polyamide resin, and various properties were examined. The results are shown in Table 1.

[0053]

Example 7 Using a-2 as a polyamide resin, flame retardant b-1, glass fiber c-1, fatty acid ester derivative d-1 of polyhydric alcohol, copper compound e-2, organic heat stabilizer f- Pellets were obtained and various properties were examined in the same manner as in Example 1 except that the compounding amount of 2 was changed to the ratio shown in Table 1. The results are shown in Table 1.

[0054]

Comparative Examples 1 and 2 Using a-2 as the polyamide resin, flame retardant b-1, glass fiber c-1, fatty acid ester derivative d-1 of polyhydric alcohol, copper compound e-2 and organic heat stabilizer. Pellets were obtained in the same manner as in Example 1 except that the compounding amount of f-2 was changed to the ratio shown in Table 1, and various properties were examined. The results are shown in Table 1.

[0055]

Example 8 48.4% by weight of polyamide resin a-2,
Flame retardant b-2 is 25.0% by weight, glass fiber c-1 is 2
5.0 wt%, fatty acid ester derivative d-1 of polyhydric alcohol 1.5 wt%, copper compound e-2 0.029 wt%, organic heat stabilizer f-2 0.1 wt% Using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.), the cylinder set temperature is 240 ° C., the screw rotation is 100 rpm,
Under the condition that the discharge rate is 30 kg / hr, the polyamide resin a-
2, flame retardant b-1, polyhydric alcohol fatty acid ester derivative d-1, copper compound e-2 and organic heat stabilizer f-
2 was top-fed and the glass fiber c-1 was side-fed and kneaded, taken out in a strand form, cooled and granulated with a cutter to obtain a polyamide resin composition pellet.
Various characteristics of the obtained pellet were examined by the above-described measuring method. The results are shown in Table 2.

[0056]

Example 9 Pellets were obtained in the same manner as in Example 8 except that the flame retardant was b-1, and the copper compound e-1 was used in place of the copper compound e-2, and various properties were examined. The results are shown in Table 2.

[0057]

[Example 10] Organic heat stabilizer f with flame retardant b-1
-2, pellets were obtained in the same manner as in Example 8 except that the organic heat stabilizer f-1 was used and the compounding amount was changed to the ratio shown in Table 2, and various characteristics were examined. The results are shown in Table 2.

[0058]

[Example 11] Organic heat stabilizer f with flame retardant b-1
-2, pellets were obtained in the same manner as in Example 8 except that the organic heat stabilizer f-3 was used and the compounding amounts were changed to the proportions shown in Table 2, and various characteristics were examined. The results are shown in Table 2.

[0059]

Example 12 Pellets were obtained in the same manner as in Example 8 except that the organic heat stabilizer f-2 was used in place of the organic heat stabilizer f-2 and the blending amount was changed to the ratio shown in Table 2. , Various characteristics were investigated. The results are shown in Table 2.

[0060]

COMPARATIVE EXAMPLE 3 Example 8 except that the compounding amounts of the polyamide resin a-2, the flame retardant b-1 and the glass fiber c-1 were set to the ratios shown in Table 2 with the copper compound and the organic heat stabilizer being 0. Pellets were similarly obtained and various properties were examined. The result is 2.

[0061]

Comparative Example 4 Pellets were obtained in the same manner as in Example 8 except that the flame retardant b-1 was used and the amounts of the copper compound e-2 and the organic heat stabilizer f-2 were changed to the ratios shown in Table 2. , Various characteristics were investigated. The result is 2. As can be seen from Examples 1 to 12 and Comparative Examples 1 to 4, an adduct formed from a reinforced polyamide resin with a specific amount of melamine and phosphoric acid, a specific amount of a fatty acid ester derivative of a polyhydric alcohol, a specific amount. Only when the copper compound and the specific amount of the organic heat stabilizer are combined, it is possible to satisfy all the properties of thin-wall flame retardancy, mechanical properties, and heat aging resistance.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

EFFECTS OF THE INVENTION The composition of the present invention has extremely high flame retardancy even in a thin-walled molded product, does not generate highly corrosive hydrogen halide gas during combustion, and retains excellent mechanical properties and toughness. It is also a molding material that also has excellent heat aging resistance, and can be used for home appliances, electronic parts, automobile parts and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 CL011 CL031 CL051 DA017                       DC007 DD079 DD089 DE187                       DE189 DE237 DF009 DG007                       DG049 DG057 DH026 DH049                       DJ007 DJ017 DJ037 DJ047                       DJ057 DL007 DM007 EG019                       EG079 EH058 EJ029 EJ039                       EJ049 EJ069 EL099 EL129                       EN069 EP029 EU079 EU089                       EU186 EU189 EV079 EV249                       EW069 EW089 EW119 EW129                       FA047 FA087 FD017 FD049                       FD079 FD136 GN00 GQ00

Claims (11)

[Claims] 1. An adduct 5 formed from (a) 30 to 85% by weight of polyamide resin and (b) melamine and phosphoric acid.
˜40% by weight, (c) inorganic filler 5 to 50% by weight,
(D) Polyalkylene polyhydric alcohol and 10 to 3 carbon atoms
0.01 to 5% by weight of a monoester derivative with a higher fatty acid of 0, (e) a copper compound 0.0003 to 0.1% by weight and (f) an organic heat stabilizer 0.01 to 0.5% by weight, A heat-resistant flame-retardant resin composition comprising the respective components of (a) to (f), and the total amount of the indicated weight% is 100% by weight. 2. The polyamide resin (a) is polyamide 6
6, polyamide 6, polyamide 610, polyamide 61
2. The heat-resistant flame-retardant resin composition according to claim 1, comprising at least one selected from the group consisting of 2, polyamide 6I (polyhexamethylene isophthalamide), MXD6 nylon, and copolyamides thereof. 3. The polyamide resin (a) comprises the following (1) to
The heat-resistant flame-retardant resin composition according to claim 1, comprising at least one selected from (4). (1) Polyamide 66 unit 70 to 95% by weight and polyamide 6I (polyhexamethylene isophthalamide) unit 5
(2) Polyamide 66 units 60 to 89% by weight, polyamide 6I units 5 to 30% by weight, and aliphatic polyamide units (excluding polyamide 66 units) 1 to 10% by weight. A mixed terpolymer (3) consisting of 70 to 95% by weight of polyamide 66 and 5 to 30% by weight of polyamide 6I, and (4) 60 to 89% by weight of polyamide 66 and 5 to 30% by weight of polyamide 6I, and Mixed polyamide with 1 to 10% by weight of aliphatic polyamide unit (excluding polyamide 66 unit) 4. The heat resistance difficulty according to claim 1, wherein (a) the relative viscosity of sulfuric acid of the polyamide resin (measured by JIS K6810) is 1.5 to 3.5. Fuel resin composition. 5. The (e) copper compound is copper phosphate, copper acetate,
The heat-resistant flame-retardant resin composition according to any one of claims 1 to 4, which is at least one copper compound selected from copper iodide. 6. The organic heat stabilizer (f) is at least one organic heat stabilizer selected from phosphorus-based stabilizers, amine-based stabilizers, and phenol-based stabilizers. The heat-resistant flame-retardant resin composition according to any one of 1 to 5. 7. (d) An ester derivative of a polyalkylene polyhydric alcohol and a higher fatty acid having 10 to 30 carbon atoms,
7. A higher fatty acid monoester derivative of at least one polyhydric alcohol selected from polyethylene glycol monolaurate, polyethylene glycol monostearate and polyethylene glycol monooleate, according to any one of claims 1 to 6. Reinforced flame-retardant polyamide resin composition. 8. (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 heat-resistant flame-retardant resin composition according to any one of claims 1 to 7. 9. The phosphorus-based flame retardant comprises 10 to 10 phosphorus atoms.
The heat-resistant flame-retardant resin composition according to claim 8, containing 18% by weight. 10. The average particle size of the phosphorus-based flame retardant is 0.5 to 0.5.
It is 20 micrometers, The heat resistant flame-retardant resin composition of Claim 8 characterized by the above-mentioned. 11. The inorganic filler (c) is at least one type of reinforcing material selected from glass fiber, wollastonite, talc, calcined kaolin, and mica. The heat-resistant flame-retardant resin composition according to any one of 1.