JPH06345963A - Flame-retardant polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in heat resistance, mechanical properties, flame retardancy, and thermal stability during injection molding by incorporating a brominated polystyrene and a hydrotalcite into a nylon 4, 6 resin. CONSTITUTION:This resin composition comprises 10-96.9wt.% nylon 4, 6 resin, 0-40wt.% aromatic polyester, 1-50wt.% brominated styrene (co)polymer, 1-20wt.% flame retardant aid, 1-50wt.% filler 0.01-10wt.% hydrotalcite, and 0-40wt.% at least either a copolymer of an olefinic polymer with an unsaturated carboxylic acid (derivative) or a hydrogenated styrene/butadiene block copolymer modified with an unsaturated carboxylic acid (derivative). It is excellent in heat resistance, mechanical properties, flame retardancy, and thermal stability during injection molding.

Description

Detailed Description of the Invention

[0001]

The present invention relates to heat resistance, mechanical properties,
The present invention relates to a polyamide resin composition having excellent flame retardancy and thermal stability during injection molding.

[0002]

2. Description of the Related Art In the field of electronic parts, various resin-based electronic parts materials (connectors, switches, relays, coil bobbins, etc.) have been surface-mounted (SMT) in accordance with the recent miniaturization of electric and electronic products and improvement in productivity. The number of cases of soldering on a printed circuit board is increasing. When connecting the parts on the printed circuit board by the surface mounting method,
Soldering is carried out in a reflow oven such as a hot-air type or a far-infrared type, and the parts are under severer temperature conditions than the conventional mounting method using a solder bath. Therefore, as a resin material for these electronic parts, conventional materials such as polyamide resins such as nylon 6 resin and nylon 66 resin, polyester resins such as polyethylene terephthalate and polybutylene terephthalate have insufficient heat resistance,
A resin material for surface mounting having high heat resistance was desired.

Nylon 4,6 resin has a high melting point (295
C.) and good mechanical properties, a composition containing a halogenated compound represented by nylon 4,6 resin, brominated polystyrene and the like and a metal oxide as a main component is particularly promising for the above applications. And is proposed (JP 61
-188463, JP 62-201964, 63-51.
456, 63-118368, 63-128073, 6
3-139942, 63-161056, 63-223
060, 63-317552, etc.).

However, a blend of nylon 4,6, a halogenated compound typified by brominated polystyrene and a metal oxide has a processing temperature of nylon 4,6 of 2 or more.
Since the temperature is as high as 90 to 330 ° C., decomposition of a halogenated compound typified by brominated polystyrene causes melting and pelletizing in an extruder, retention during injection molding,
There is a problem that molding defects such as discoloration and burning occur due to changes in molding conditions, and improvements have been demanded. Further, in order to improve water absorption of nylon 4,6 and blisters when passing through reflow at the time of water absorption, a composition comprising nylon 4,6, polymethylene terephthalate, brominated polystyrene, a flame retardant aid and glass fiber is used. JP-A-3-19096
Although proposed in Japanese Patent Laid-Open No. Hei 3-263461, there are similar problems, and improvements have been demanded.

As a method for improving the thermal stability at the time of melt molding in a flame-retardant polyamide using an organic halogen compound as a flame retardant, JP-A-2-142852 discloses:
It has been proposed to add one or both of hydrotalcites and magnesium / aluminum compounds to polyamide resin, fibrous inorganic reinforcing material, halogenated polystyrene or halogenated polyphenylene ether, and flame retardant aid. . However, with this method, since the processing temperature of nylon 4,6 resin is high, although discoloration, burning, foaming, etc. during normal molding are reduced,
Sufficient effects were not obtained for discoloration, burning, foaming, etc. that occur when the product stays in the injection molding machine or when a molding machine having a large injection capacity relative to the weight of the molded product is used.
Further, even when the flame-retardant nylons 4 and 6 were pelletized using the twin-screw extruder, the change in color tone due to the change in extrusion conditions was large.

[0006]

Therefore, the inventors of the present invention have made halogens excellent in heat stability without deterioration such as discoloration or burning of pellets or molded articles due to retention during melt mixing of the compound and injection molding. As a result of studying to obtain a flame retardant-containing nylon 4,6 resin composition, it was found that the above object can be solved by combining a specific brominated polystyrene polymerized from a dibrominated styrene monomer and hydrotalcites. Invented.

[0007]

That is, the present invention is
(A) Nylon 4,6 resin 10-96.9% by weight,
(B) Aromatic polyester 0 to 40% by weight, (C) Brominated styrene (co) polymer 1 to 50% by weight, (D) Flame retardant auxiliary agent 1 to 20% by weight, (E) Filler 1 to 50% weight%,
(F) 0.01 to 10% by weight of hydrotalcite stabilizer, and (G) an olefin polymer (G1) containing an unsaturated carboxylic acid or a derivative thereof as a copolymer component and / or an unsaturated carboxylic acid or Hydrogenated styrene-butadiene block copolymer modified with its derivative (G2)
A flame-retardant polyamide resin composition comprising 0 to 40% is provided.

The present invention will be described below according to its constituent features. (A) Nylon 4,6 Resin Nylon 4,6 resin (hereinafter referred to as “nylon 4,6”) used in the present invention includes polytetramethylene adipamide and polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid. It includes a copolyamide having a tetramethylene adipamide unit as a main constituent. Further, other polyamide may be contained as a mixed component within a range not impairing the properties of nylons 4 and 6. The copolymerization component is not particularly limited, and a known amide-forming component can be used. As a typical example of the copolymerization component, 6-aminocaproic acid, 11-
Amino acids such as aminoundecanoic acid, 12-aminoundecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bis (aminomethyl) cyclohexane,
1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (aminoprosyl) Diamines such as piperazine and aminoethylpiperazine and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5 -Sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, dicarboxylic acids such as diglycolic acid and the like can be mentioned.

Nylon 4,6 used in the present invention
The manufacturing method of is arbitrary. For example, JP-A-56-149
430, JP-A-56-149431, JP-A-58-83029 and JP-A-61-4363.
No. 1, etc., that is, first, a prepolymer having a small amount of cyclic end groups is produced under specific conditions, and then solid-state polymerized in a steam atmosphere to obtain high-viscosity nylon 4,
6 or a method of obtaining it by heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone. The degree of polymerization of nylon 4 and 6 is not particularly limited, but in 25%, 96% sulfuric acid, 1 g / dl
Nylon 46 having a relative viscosity in the range of 2.0 to 6.0 is preferably used. The blending amount of nylon 4,6 in the present invention is 10 to 96.9% by weight,
Preferably 10-70% by weight, more preferably 15-
It is 60% by weight. If the addition amount of nylon 4 or 6 is less than 10% by weight, the workability of the component is problematic, and if it exceeds 96.9% by weight, the blister resistance is poor.

(B) Aromatic Polyester The aromatic polyester used in the present invention has an acid component of terephthalic acid or 2,6-naphthalenedicarboxylic acid, and a diol component of ethylene glycol, propylene glycol, tetramethylene glycol, hexa It is a polyester composed of at least one kind such as methylene glycol. Among these, polybutylene terephthalate and polyethylene terephthalate whose acid component is terephthalic acid, and polyethylene-2,6-naphthalene dicarboxylate and polytetramethylene-2 whose acid component is 2,6-dinaphthalenecarboxylic acid, 6-Dinaphthalenecarboxylate, poly (1,4-dicyclohexylene dimethylene terephthalate) whose acid component is 1,4-cyclohexylene dicarboxylic acid, and the like are preferable. The aromatic polyester may be a polyester obtained by substituting a part of the above polyester with another copolymerization component, and examples of such a copolymerization component include isophthalic acid, phthalic acid, methylterephthalic acid and methylisophthalic acid. Derivatives of phthalic acid; 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene carboxylic acid and other naphthalene dicarboxylic acids and their derivatives;
-Diphenylcarboxylic acids such as didiphenylcarboxylic acid and 3,4'diphenylcarboxylic acid and derivatives thereof;
4,4'-diphenoxymethanedicarboxylic acid, 4,4 '
Aromatic dicarboxylic acids such as diphenoxyethanecarboxylic acid; Aliphatic or alicyclic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid; 1,4-cyclohexanedimethanol, etc. Alicyclic diols, hydroquinones, resorcin and other dihydroxybenzenes and derivatives; 2,2'-bis (4-hydroxyphenyl)
Bisphenol compounds such as propane and 2,2-bis (4-hydroxyphenyl) sulfone; ether diols obtained from bisphenol compounds and glycols such as ethylene glycol; ε-oxycaproic acid, hydroxybenzoic acid, hydroxyethoxybenzoic acid, etc. Examples thereof include oxydicarboxylic acid. In addition, the aromatic polyester described above has a branched component, for example, tricarballylic acid,
1. An acid having a trifunctional or tetrafunctional ester forming ability such as trimesic acid or trimellitic acid, or an alcohol having a trifunctional or tetrafunctional ester forming ability such as glycerin, trimethylolpropane or pentaerythritol.
You may copolymerize 0 mol% or less.

The intrinsic viscosity number of the aromatic polyester used in the present invention is preferably 0.5 or more, and more preferably 0.6 or more when measured at 35 ° C. using o-chlorophenol. The aromatic polyester used in the present invention can be produced by a usual production method, for example, a melt polycondensation reaction or a method in which this is combined with a solid phase polycondensation reaction. The addition amount of the aromatic polyester used in the present invention is 0 to 40% by weight, preferably 5 to 40% by weight, particularly preferably 5 to 3% by weight in order to obtain a composition having low hydrogen absorption.
It is 0% by weight. If it exceeds 40% by weight, the mechanical strength will be poor.

(C) Brominated Styrene (Co) Polymer The brominated styrene (co) polymer used in the present invention is
A polybrominated styrene produced by (co) polymerizing a monomer of brominated styrene such as dibrominated styrene, a typical example of which is a structural unit represented by the following general formula (I) as a main constituent component. Polybrominated styrene having a weight average molecular weight of 1,000 to 300,000 is preferably used. The brominated styrene is preferably a nucleus-substituted brominated styrene, and the bound bromine is preferably 2 to 5, more preferably 2 to 3, and particularly preferably 2.

[0013]

[Chemical 1]

(In the above general formula, n is an integer of 2 or more and m is an integer of 2 to 5.) Further, the general formula (I) can be used even if another vinyl compound is copolymerized. is there. Examples of other vinyl compounds include styrene, methylstyrene, acrylonitrile, maleic anhydride, and (meth) acrylic acid ester. In the composition of the present invention, the addition amount of the component (C), polybrominated styrene, is 1 to 5
It is 0% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight. If the addition amount is less than 1% by weight, the flame retarding effect of the composition of the present invention is not sufficient, and if it exceeds 50% by weight, mechanical properties and thermal properties are impaired, which is not preferable.

(D) Flame Retardant Auxiliary Agent The flame retardant auxiliary agent used in the present invention functions to enhance the flame retardancy of nylon 4,6 resin by a synergistic effect with the flame retardant agent. Such compounds include, for example, Va of the Periodic Table.
Examples thereof include metal compounds of group I and boron oxide, zirconium oxide, iron oxide, zinc oxide, and the like, and antimony compounds are particularly preferable as the metal compound of group Va of the periodic table. As the antimony compound, antimony trioxide,
Examples thereof include antimony pentaoxide and sodium antimonate, and antimony trioxide is particularly preferably used. Further, only one kind of these flame retardant aids may be blended or two or more kinds thereof may be used in combination. The amount of the flame retardant aid added in the present invention is 1 to 20% by weight, preferably 2 to 15%.
%, More preferably 3 to 10% by weight. The amount of these flame retardant aids to be compounded is 1 to 1 atom of metal such as antimony to 2 to 5 of bromine atom of brominated polystyrene as the component (C). When is preferred.

(E) Filler As an example of the filler used in the present invention, glass fiber,
Carbon fiber, aromatic polyamide fiber, steel fiber asbestos, ceramic fiber, potassium titanate whiskers,
Fibrous fillers such as boron whiskers, calcined kaolin,
Examples thereof include powdery, granular, or plate-like inorganic fillers such as talc, mica, calcium carbonate, barium sulfate, glass beads, and glass flakes. These fillers may be used alone or in combination of two or more. Among the above fillers, glass fiber or calcined kaolin is preferably used. The type of glass fiber is not particularly limited as long as it is used for general resin reinforcement, and for example, long fiber type or short fiber type chopped strand, milled fiber, etc. can be selected and used. The glass fiber is preferably treated with a sizing agent (polyvinyl acetate, ethylene / vinyl acetate copolymer, polyurethane, acrylic urethane, polyester, etc.) and a coupling agent (aminosilane, acrylsilane, vinylsilane, epoxysilane, etc.). The calcined kaolin is not particularly limited as long as it is used for general resin reinforcement, but the average particle diameter is preferably 10 microns or less, and particularly preferably 2 microns or less. The calcined kaolin is also preferably surface-treated with an organic silane compound such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane. The addition amount of the filler of the present invention is 1 to 50% by weight, preferably 2 to 4
5% by weight, more preferably 5 to 40% by weight, 1
If it is less than 50% by weight, the reinforcing effect on the tensile strength by the filler does not appear, and if it exceeds 50% by weight, problems particularly occur in extrusion moldability and injection moldability.

(F) Hydrotalcite Compounds The hydrotalcite compounds used in the present invention have the following general formula (II): Mg _1-x Al _x (OH) _{2 An} ^- _{x / 2} · mH ₂ O ... The hydrotalcites represented by (II) can be mentioned. However, in the formula (II), A ⁿ⁻ represents an n-valent anion, and x and m represent numbers represented by the following formula. 0 <x ≦ 0.5, 0 <m <1 In the above formula (II), preferred examples of the n-valent anion represented by A ⁿ⁻ are CO ₃ ²⁻ , HPO ₄ ⁻ , SO ₄ ^2−. ,
OH ^{− and the} like can be mentioned. The hydrotalcites have a BET specific surface area of 1 to 25 m ² / g, preferably ^{2 to 20} m ² / g, and an average particle size of 5 microns or less, preferably 3 microns or less. Such hydrotalcites include natural and synthetic ones, both of which can be used in the present invention. The addition amount of the hydrotalcite stabilizer used in the present invention is 0.01 to 10% by weight.
It is preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.

The composition of the present invention is unsaturated for the purpose of improving the ductility and toughness of the composition of the present invention or for enhancing the compatibility of the components (A) and (B) in the composition of the present invention. An olefin polymer (G1) containing a carboxylic acid or its derivative as a copolymer component, and / or a hydrogenated styrene-butadiene block copolymer (G2) modified with an unsaturated carboxylic acid or its derivative (G component). )
Is preferably added.

In the component (G1), examples of the unsaturated carboxylic acid or its derivative include maleic acid, maleic acid ester, maleic acid amide, maleic anhydride, methyl maleic anhydride, chloromaleic anhydride and citraconic anhydride. Butynyl succinic anhydride, tetrahydrophthalic anhydride, fumaric acid, fumaric acid ester, fumaric acid amide,
Fumaric acid imide, phthalic acid, itaconic acid, itaconic anhydride, itaconic acid ester, itaconic acid amide, itaconic acid imide, halogenated maleic acid, crotonic acid, acrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate , 2-hydroxyethyl acrylate, glycidyl acrylate, methyl methacrylate, methyl methacrylate, butyl methacrylate, methacrylic acid 2
-Ethylhexyl, 2-hydroxyethyl methacrylate, glycidyl methacrylate and the like can be mentioned, but maleic anhydride and glycidyl methacrylate are particularly preferable.

Examples of the olefinic unsaturated monomer which is a copolymer component of the olefinic polymer (G1) having an unsaturated carboxylic acid or a derivative thereof as a copolymerization component used in the present invention include the following. . Examples thereof include olefins such as ethylene, propylene, butene-1, decene-1, octacene-1, styrene, vinyl esters such as vinyl acetate and vinyl propionate, and ethylene is particularly preferable. These monomers and unsaturated carboxylic acids or derivatives may be used alone or in the form of a copolymer. The content of these unsaturated carboxylic acids or their derivatives is
1) 0 to 40% by weight, preferably 1 to 30% by weight, more preferably 3 to 25% by weight, particularly preferably 3 to 20% by weight, based on 100% by weight.

In the component (G2), hydrogenated styrene-
A butadiene block copolymer is obtained by hydrogenating a block copolymer composed of a vinyl aromatic compound polymer block and a polymer block containing a conjugated diene compound as a main component. Can be produced by selectively hydrogenating to an extent not exceeding 20% to obtain a vinyl aromatic compound polymer block A and a block B having a degree of unsaturation not exceeding 20%. The component (G2) is
It can be obtained by adding a carboxylic acid group or its derivative to such a hydrogenated styrene-butadiene copolymer. In the modified hydrogenated styrene / butadiene block copolymer (G2), the content of the vinyl aromatic compound polymer is preferably in the range of 10 to 42% by weight, more preferably 15 to 25% by weight. is there. When the content of the vinyl aromatic compound polymer block A in the modified block copolymer exceeds 42% by weight, the tensile elongation at break of the composition of the present invention becomes small and the ductility (tensile elongation at break) is not sufficiently increased. It is not preferable. On the other hand, if the content of the block copolymer A is less than 10% by weight, the strength and rigidity of the compounded composition are lowered, which is not preferable.

Examples of vinyl aromatic hydrocarbons constituting the block copolymer before hydrogenation include styrene and α-
Methylstyrene, vinyltoluene, vinylnaphthalene and the like can be mentioned, but styrene is particularly preferable. As the conjugated diene compound, for example, 1.3-butadiene,
Examples include 1,3-pentadiene and isoprene, with 1.3-butadiene being particularly preferred.

The number average molecular weight of the block copolymer is 1
The range of 50,000 to 500,000 is preferable, and the range of 20,000 to 100,000 is more preferable. Block copolymers are usually anionic living compounds in which a vinyl aromatic compound and a conjugated diene compound are used as monomers in an inert hydrocarbon solvent such as benzene, toluene, or cyclohexane, using an organolithium compound such as butyllithium as a catalyst. Although it is synthesized by a polymerization method, it is not particularly limited as long as it is synthesized by any means as long as it falls within the above range. By hydrogenating the above block copolymer by a known method, for example, the method described in JP-B-42-8704, a portion not exceeding 20% of the aromatic double bond of the vinyl aromatic compound A is obtained. , And a partially hydrogenated block copolymer in which at least 80% of the aliphatic double bonds of the conjugated diene compound block B are hydrogenated. The unsaturation degree of the block B in the present invention is a ratio of carbon-carbon double bonds contained in the block B, and this is determined by a conventionally known technique such as an iodometric titration method.

The hydrogenated block copolymer is then modified by addition reaction with a molecular unit containing a carboxylic acid group or its derivative. The addition amount of the molecular unit containing a carboxylic acid group or its derivative group to the hydrogenated block copolymer is preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the hydrogenated block copolymer, -5 parts by weight are particularly preferred. When the addition amount is 0.01 parts by weight or less,
When the composition is used, the effect of modification is not sufficient, and when it exceeds 20 parts by weight, unfavorable results such as coloring of the blended polyamide resin and reduction of the molecular weight are obtained. The addition reaction of a molecular unit containing a carboxylic acid group or a derivative thereof to the hydrogenated block polymer can be carried out by a conventionally known method, in the presence or absence of a solvent and in the presence of a radical generator. It is preferable to do this. As the radical generator used in the addition reaction, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy)
3,3,5-Trimethylcyclohexane, 2,5-dimethyl-di (t-butylperoxy) hexane and the like can be used.

Specific examples of an olefin polymer containing an unsaturated carboxylic acid or its derivative as a copolymer component or a hydrogenated block copolymer modified with an unsaturated carboxylic acid or its derivative include ethylene / glycidyl methacrylate copolymer. Coal, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid / maleic anhydride copolymer,
Ethylene / maleic acid copolymer, ethylene / ethyl acrylate / acrylic acid copolymer, styrene / maleic anhydride copolymer, ethylene-g-maleic anhydride copolymer (g represents a graft), ethylene / propylene -G-
Examples thereof include a maleic anhydride copolymer, a maleic anhydride modified hydrogenated styrene / butadiene block copolymer, and a glycidyl methacrylate modified hydrogenated styrene / butadiene block copolymer. The addition amount of the olefin polymer having the unsaturated carboxylic acid or its derivative as a copolymerization component of the present invention or the hydrogenated block copolymer modified with the unsaturated carboxylic acid or its derivative is 0 to 40% by weight, preferably Is 1 to 30% by weight, more preferably 2 to
20% by weight, particularly preferably 2 to 10% by weight.

The composition of the present invention further comprises a copper compound such as copper iodide, an aromatic amine compound, a hindered phenol compound, an organophosphorus compound for the purpose of improving heat resistance.
Antioxidants such as sulfur compounds or heat stabilizers can also be added. In addition, if necessary, other components, for example, a pigment, as long as the moldability and physical properties are not impaired.
Dyes, ultraviolet absorbers, weathering agents, lubricants, crystal nucleating agents, release agents, plasticizers, antistatic agents and the like may be added. Furthermore, small amounts of other thermoplastic resins such as other polyamide resins, polyphenylene ether resins, polycarbonate resins, phenoxy resins, polyethylene and copolymers thereof, polypropylene and copolymers thereof, styrene and copolymers thereof. , Polystyrene and its copolymers, acrylic resins and acrylic polymers, and polyamide elastomers may be blended.

Any compounding method can be used to obtain the resin composition of the present invention. For example, a batch mixer such as a kneader, a Brabender, a Banbury mixer, or a single-screw or twin-screw extruder is used to simultaneously or separately prepare each component of the present invention, for example, 2-3 components are preliminarily prepared in a blender or the like in advance. A method of blending or premixing with a kneader or an extruder and further mixing the remaining components and homogenizing can be used.

Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the pellet color tone, tensile property, bending property, flame retardancy, and retention stability in Examples and Comparative Examples were measured by the following measuring methods.

Pellet color tone When the resin composition was melt-kneaded with a twin-screw extruder and pelletized, the color tone and state of the pellets were evaluated as follows. Color tone (good) White ＞ Light beige ＞ Beige ＞ Dark beige ＞ Brown (defective) Condition ○: Good pellet tightness, △: Somewhat poor,
X: Poor (with space inside) Tensile property According to ASTM D638. Bending property According to ASTM D790. Flame Retardant Underwriters Laboratory
atory; hereinafter, abbreviated as "UL"), a combustion test (Vertical Test) was performed using a test piece having a thickness of 1/32 inch according to the UL-94 test method of V-O or V-
2 was judged. However, in the combustion test, V-0 means that there is no melt dripping of the resin, or that there is melt dripping of the resin but the cotton placed below is not ignited, and V-2 means that there is a flame. This is the case when there is melting and dropping of the resin and the cotton placed underneath is ignited. Residence stability Injection capacity 1 ounce, maximum mold clamping pressure 35t injection molding machine, cylinder set temperature 310 ℃, mold temperature 100 ℃,
Injection pressure 700-1200kgf / cm ² , holding time 5
Seconds, cooling time (residence time) is set to 10 seconds and 180 seconds, a molded product of 127 mm × width 12.7 mm × thickness 0.8 mm is molded, and a molded product with a cooling time of 10 seconds and a molded product of 180 seconds are compared. Then, the presence or absence of discoloration and discoloration of the molded product having a cooling time of 180 seconds was compared with that for 10 seconds, and the appearance was judged.

Each composition used in the following examples and comparative examples
Minutes will be explained.(A) component Nylon 4,6 resin: "STAN" manufactured by DSM, Netherlands
YL ", relative viscosity 3.0 at 96% sulfuric acid 1 g / dl(B) component Polybutylene terephthalate: PBT (O-chlorophenol was used to measure the limit at 35 ° C.
Viscosity number 0.6)(C) component Polybrominated styrene: Made from dibrominated styrene monomer
Polybrominated styrene produced (number average molecular weight 80,000, bromine content 59% by weight)(D) ingredient Glass fiber: Glass fiber chopped strand, fiber diameter
Urethane sizing agent and γ with 10μ and 3mm length
-Treated with aminopropyltrimethoxysilane. Calcined Kaolin: Translink manufactured by Engelhard Corporation
445, average particle size 1.4 microns, aminosilane treatment(E) ingredient Antimony trioxide: PATOX-C manufactured by Nippon Seiko Co., Ltd.(F) ingredient  Hydrotalcite: Kyowa Chemical Industry Co., Ltd., DHT-
4A-2 (molar ratio MgO / Al₂O₃= 4.3, BET specific surface area
12m²/ G)(G) component Ethylene / glycidyl methacrylate copolymer: EG
MA (Ethylene / GMA weight ratio = 85/15, 190 ° C.,
MFR value at 2.16 kgf 3 g / min) Maleic anhydride modified hydrogenated styrene / butadiene block
Copolymer: MAH-SEBS Styrene-butadiene with 30% styrene content and 38% vinyl content
Hydrogenation rate of ene / styrene (SBS) block copolymer is 9
Hydrogenated styrene / butadiene obtained by hydrogenation to 0%
2.5 parts by weight based on 100 parts by weight of the block copolymer
Maleic anhydride, 0.1 part by weight of perhexa 25B
After uniformly dry blending (manufactured by Nippon Oil & Fats), nitrogen nitrogen
It is supplied to a twin-screw extruder in an elementary atmosphere, and the cylinder temperature is 25
The reaction is carried out at 0 ° C, and unreacted maleic anhydride is removed.
Removed by heating under vacuum.Other Brominated polystyrene: manufactured by Nissan Ferro Organic Chemicals Co., Ltd.
Irocheck 68PB (produced by brominating polystyrene, bromine content 6
6%)

After mixing components other than the component (D) in advance with a tumbler according to the formulation shown in Table 1, the screw has a two-stage kneading block, and between the first-stage and second-stage kneading blocks. Supplied from the root of a 45 mmφ twin-screw extruder (Ikegai Tekko PCM45) with a feed port on the way, the filler of component (D) is fed from the feed port on the way, cylinder temperature 300-320 ° C, discharge rate 50 KG / hr, rotation speed Two
It was melt-kneaded and pelletized while drawing a vacuum under the condition of 00 RPM. Then, the obtained pellets are dried with a dehumidifying dryer, and then the injection molding machine (cylinder temperature 290 to 32) is used.
A predetermined test piece was prepared at 0 ° C.) and subjected to the test. As examples and comparative examples, Table 1 shows evaluation results of mechanical properties, retention stability and the like.

Examples 1 to 6 In Examples 1 to 6, the resin compositions obtained had good pellet color and condition when pelletized by a twin-screw extruder, and even when they stayed during injection molding, It does not cause burns or discoloration and exhibits excellent retention stability. It also exhibits good mechanical properties and heat resistance.

Comparative Examples 1-3 Compared to Examples 1-3, instead of the polybrominated styrene produced from the dibrominated polystyrene monomer of the present invention,
This is an example in which post-brominated polystyrene is used and the hydrotalcite of the present invention is not used, and the color tone and state of the pellets are inferior, and the discoloration and discoloration of the molded product occur due to retention during injection molding. Comparative Example 4 Since the polybrominated styrene of the present invention is not used, the color tone and state of pellets and the retention stability during injection molding are poor. Comparative Example 5 Since the hydrotalcite of the present invention is not used, the color tone and state of pellets and the retention stability during injection molding are poor.

[0034]

The flame-retardant polyamide resin composition of the present invention has excellent heat resistance, mechanical properties and retention stability as a resin material for surface mounting using a reflow furnace.

[Table 1]

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 67/02 LNZ

Claims (1)

[Claims] 1. (A) Nylon 4,6 resin 10 to 96.
9% by weight, (B) 0 to 40% by weight of aromatic polyester,
(C) 1 to 50% by weight of (co) polymer of brominated styrene,
(D) Flame retardant aid 1 to 20% by weight, (E) Filler 1 to 50
% By weight, (F) hydrotalcite compound 0.01 to
10% by weight, and (G) an olefin polymer (G) containing an unsaturated carboxylic acid or its derivative as a copolymer component
1) and / or a flame-retardant polyamide resin composition comprising 0 to 40% of a hydrogenated styrene-butadiene block copolymer (G2) modified with an unsaturated carboxylic acid or a derivative thereof.