JP6002464B2 - Long glass fiber reinforced flame retardant polyamide resin composition and molded article - Google Patents

Description

  The present invention relates to a long glass fiber reinforced flame retardant polyamide resin composition and a molded article.

Since polyamide resins are excellent in flame retardancy and electrical characteristics, they have been widely used for electric / electronic parts, machine parts, automobile parts and the like.
In particular, a fiber reinforced polyamide resin composition containing a fibrous inorganic reinforcing material has excellent electrical characteristics, mechanical characteristics, and molding processability, and thus is useful for reducing the weight of parts and reducing the number of parts ( For example, see Patent Documents 1 and 2.)

However, the fiber-reinforced polyamide resin composition reinforced by blending short glass fibers usually has a glass fiber length of about 0.3 mm in a molded product, and therefore, practically sufficient impact resistance cannot be obtained. Have a problem.
In order to improve the impact resistance, a fiber reinforced polyamide resin composition reinforced by blending a long fiber reinforcing material has been conventionally proposed. For example, Patent Documents 3 and 4 disclose a polyamide resin composition obtained by further adding a brominated flame retardant and an antimony compound to a fiber reinforced polyamide resin composition whose impact resistance is improved by a long fiber reinforcement. . Patent Document 5 discloses a resin composition in which a phosphorus-based flame retardant is further added as a flame retardant to a fiber-reinforced polyamide resin composition.

Japanese Patent Laid-Open No. 10-158506 Japanese Patent Laid-Open No. 2005-220240 JP 2006-193551 A JP 2009-167270 A JP 2006-181776 A

  However, all of the techniques proposed in the above cited references 3 to 5 require a blend of a long fiber reinforced polyamide resin pellet and a polyamide resin pellet containing a flame retardant (may include a short fiber reinforcing material). It is a requirement. Therefore, in any case, the pellets are classified at the time of transportation or the like, and there is a problem that the flame retardant concentration varies from product to product and the flame retardancy varies.

  Therefore, in the present invention, a glass long fiber reinforced flame retardant polyamide resin that not only has excellent mechanical strength but also has a very high flame retardancy and has a good surface appearance due to excellent moldability. An object is to provide a composition.

As a result of intensive studies to solve the above-described problems of the prior art, the present inventor has obtained a specific polyamide resin, a polyamide resin composition pellet containing a predetermined glass fiber, a higher fatty acid metal salt, and a coloring master. It discovered that the glass long fiber reinforced flame-retardant polyamide resin composition containing a batch pellet can solve the said subject, and came to complete this invention.
That is, the present invention is as follows.

[1]
Polyamide resin composition pellets,
(A): (a-1) 50 to 90% by mass of a polyamide 66 / 6I copolymer having a sulfuric acid relative viscosity (ηr) of 1.80 to 2.50 measured according to JIS K6810 , (a-2 30) to 50 parts by mass of a polyamide resin composition containing 9 to 35% by mass of a brominated flame retardant and (a-3) 1 to 15% by mass of antimony oxide;
(B): TEX number is 3000 to 4000 (TEX), monofilament average fiber diameter is 1
50 to 70 parts by mass of glass fiber having a length of 5 to 18 μm and a length of 5 to 15 mm in the polyamide resin composition pellets;
And 100 parts by mass of a polyamide resin composition pellet having a length of 5 to 15 mm,
(C): 0.01 to 0.5 parts by mass of a higher fatty acid metal salt;
(D): 1 to 10 parts by mass of colored master batch pellets;
including,
A long glass fiber reinforced flame retardant polyamide resin composition.
[2]
(A-1) The glass long fiber according to [1], wherein the ratio of 66 components of the polyamide 66 / 6I copolymer is 60 to 90% by mass and the ratio of 6I components is 10 to 40% by mass. Reinforced flame retardant polyamide resin composition.
[3]
A molded article obtained by molding the long glass fiber reinforced flame retardant polyamide resin composition according to [1] or [2].

  According to the present invention, it is possible to obtain a polyamide resin composition having excellent mechanical strength, extremely high flame retardancy, and excellent moldability, and a molded article having a good surface appearance.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

[Glass long fiber reinforced flame retardant polyamide resin composition]
The long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment is
A polyamide resin composition pellet containing the following (A) and (B):
(A): (a-1) 50-90% by mass of polyamide 66 / 6I copolymer having a sulfuric acid relative viscosity (ηr) of 1.80-2.50, (a-2) bromine-based flame retardant 9-35 30-50 parts by mass of a polyamide resin composition containing 1% by mass and 1 to 15% by mass of (a-3) antimony oxide;
(B): 50 to 70 parts by mass of glass fibers having a TEX number of 3000 to 4000 (TEX), an average fiber diameter of monofilaments of 15 to 18 μm, and a length of 5 to 15 mm in the polyamide resin composition pellets; ,
And 100 parts by mass of a polyamide resin composition pellet having a length of 5 to 15 mm,
(C): 0.01 to 0.5 parts by mass of a higher fatty acid metal salt;
(D): 1 to 10 parts by mass of colored master batch pellets;
including,
It is a long glass fiber reinforced flame retardant polyamide resin composition.

((A) polyamide resin composition)
The polyamide resin composition pellets constituting the long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment may be described as (A) polyamide resin composition (hereinafter referred to as component (A), (A). The (A) polyamide resin composition contains the following (a-1) polyamide 66 / 6I copolymer (hereinafter sometimes referred to as (a-1)), (a-2) It contains a brominated flame retardant (hereinafter sometimes referred to as (a-2)) and (a-3) antimony oxide (hereinafter sometimes referred to as (a-3)).
(A) The polyamide resin composition can be obtained by melt-kneading the above (a-1), (a-2), (a-3) and other additives described later as necessary with an extruder.

<(A-1) Polyamide 66 / 6I Copolymer>
The (a-1) polyamide 66 / 6I copolymer is a polyamide obtained by polymerizing adipic acid, isophthalic acid, and hexamethylenediamine. In addition to these, polyamide components such as polyamide 6, polyamide 66, polyamide 66/6 copolymer, polyamide 66 / 6I / 6 copolymer, adipic acid, cyclohexanedicarboxylic acid, isophthalic acid and hexamethylenediamine Polyamide obtained by polymerizing (polyamide 66 / 6C / 6I copolymer) or the like may be contained.
The content of polyamide components other than these polyamide 66 / 6I is preferably 20% by mass or less in (a-1).
Copolymerization ratio of semi-aromatic polyamides such as polyamide 66 / 6I and polyamide 66 / 6I / 6C, and blends of the semi-aromatic polyamides and aliphatic polyamides such as polyamide 6, polyamide 66 and polyamide 66/6 By appropriately controlling the crystallization temperature by adjusting the blending ratio, glass fibers tend not to be exposed on the surface of the molded product, which is suitable for obtaining a molded product having an excellent surface appearance. As the (a-1), polyamide 66 / 6I copolymer alone is preferable.

The sulfuric acid relative viscosity (ηr) of the (a-1) polyamide 66 / 6I copolymer is in the range of 1.80 to 2.50. The range is preferably 1.85 to 2.45, more preferably 1.90 to 2.35. When the (a-1) polyamide 66 / 6I copolymer in such a range is used, the resin impregnation property of the pellet, that is, the (a-1) polyamide resin impregnation property in the polyamide resin composition pellet is excellent. Therefore, a molded product having excellent operability during extrusion and excellent surface appearance can be obtained.
The sulfuric acid relative viscosity (ηr) was measured using an Ostwald viscometer (a-1) the number of seconds of dripping of the polyamide resin solution and the number of seconds of dripping of the sulfuric acid solution under a temperature condition of 25 ° C., and the measured values were used. The following formula can be used.
In the following formula, the polyamide resin is (a-1) a polyamide 66 / 6I copolymer.
Sulfuric acid relative viscosity (ηr) = (Polyamide resin solution dropping seconds) / (Sulfuric acid solution dropping seconds)
Here, the polyamide resin solution in the formula is obtained by dissolving the polyamide resin in a 96% sulfuric acid solution to a concentration of 0.01 g / mL.

  Further, (a-1) the polyamide 66 / 6I copolymer preferably has a ratio of 66 components of 60 to 90% by mass from the viewpoint of the surface appearance of the molded product, heat resistance, and extrusion temperature, More preferably, it is 88 mass%, It is more preferable that it is 65-85 mass%, It is preferable that the ratio of 6I component is 10-40 mass%, It is more preferable that it is 12-38 mass%, More preferably, it is 15-35 mass%.

<(A-2) Brominated flame retardant>
The (a-2) brominated flame retardant is not limited to the following, but, for example, brominated polystyrene, brominated styrene maleic anhydride polymer, brominated polyphenylene ether, brominated epoxy resin, brominated Examples include crosslinked aromatic polymers and brominated phenoxy resins, and brominated polystyrene and brominated polyphenylene ether are particularly preferable from the viewpoints of heat resistance and non-bleed out properties. These (a-2) brominated flame retardants may be used alone or in combination of two or more.

<(A-3) Antimony oxide>
Examples of (a-3) antimony oxide include, but are not limited to, antimony oxides such as diantimony trioxide, diantimony tetroxide, diantimony pentoxide, and sodium antimonate.
Each of these may be used alone or in combination of two or more.
The average particle diameter of the antimony oxide (a-3) is in the range of 0.01 to 50 μm from the viewpoint of obtaining a polyamide resin composition pellet that suppresses fiber breakage during molding and has excellent mechanical strength and flame retardancy. Is preferred. More preferably, it is 0.1-30 micrometers, More preferably, it is 1-20 micrometers.
(A-3) As a measuring method of the average particle diameter of antimony oxide, there is a method of analyzing with a scanning electron microscope, measuring 100 to 200 particle diameters thereof, and determining the average particle diameter from the measured values. Can do.

<Other additives>
(A) In the polyamide resin composition, in addition to the above (a-1) to (a-3), the (a-1) polyamide 66 / 6I copolymer and the (a-2) brominated flame retardant It is also possible to use an admixture that acts between the two.
The admixture is particularly preferably a polyphenylene ether resin having an acid anhydride structure as a part of a substituent or a copolymer of styrene and maleic anhydride.
When a small amount of these admixtures is used, high strength can be obtained at the weld portion of the injection molded product.
Furthermore, the dispersed particle diameter of the (a-2) brominated flame retardant can be controlled to be small, and a molded product having toughness can be obtained.

<Combination ratio of (a-1) to (a-3)>
(A) In the polyamide resin composition, the blending ratio of (a-1) to (a-3) is (a-) with respect to 100% by mass of the total of (a-1) to (a-3). 1) 50 to 90% by mass, (a-2) 9 to 35% by mass, (a-3) 1 to 15% by mass, preferably (a-1) 55 to 85% by mass, (a-2) 12 to 33% by mass, (a-3) 3 to 13% by mass, more preferably (a-1) 60 to 80% by mass, (a-2) 15 to 30% by mass, (a-3) 5 to 10% by mass.
By setting the blending ratio of (a-1) to (a-3) within the above range, not only is excellent in continuous productivity, but also excellent in flame retardancy, and (a-2) from a brominated flame retardant Burns of the molded product due to the generated gas can be reduced, and a molded product excellent in surface appearance can be obtained.

<(A) Mixing ratio of polyamide resin composition>
In the polyamide resin composition pellets constituting the long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment, the blending ratio of the (A) polyamide resin composition is from the viewpoint of mechanical strength and appearance of the molded product. 30 to 50 parts by mass, preferably 35 to 45 parts by mass, and more preferably 40 to 45 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B) described later. .

((B) Glass fiber)
The polyamide resin composition pellets constituting the long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment contain (B) glass fibers (hereinafter sometimes referred to as (B) component).
(B) The glass fiber has a TEX number of 3000 to 4000, an average fiber diameter of monofilaments of 15 to 18 μm, a length in the polyamide resin composition pellet of 5 to 15 mm, and a polyamide resin composition pellet It is preferable to have substantially the same length.
(B) Glass fiber is used as a glass fiber roving bundle which is a continuous fiber in the stage of producing the polyamide resin composition pellets, and (A) polyamide is used as a reinforcing material by cutting and pelletizing strands. It is contained in the resin.

The glass fiber roving is preferably surface-treated with a sizing agent for polyamide resin. The sizing agent preferably contains a sizing component for the purpose of sizing and a surface treatment component for the purpose of adhesion between the polyamide resin.
The constituent components of the sizing agent for glass fiber roving are not particularly limited. Preferred sizing agents include those mainly composed of a copolymer of maleic anhydride and an unsaturated monomer and a silane coupling agent from the viewpoint of improving mechanical properties.
The copolymer of maleic anhydride and unsaturated monomer constituting the sizing agent is not limited to the following, but examples thereof include styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2, 3 -Copolymers of unsaturated monomers such as dichlorobutadiene, 1,3-pentadiene, cyclooctadiene and maleic anhydride. Among these, a copolymer of butadiene or styrene and maleic anhydride is particularly preferable. Two or more of these monomers may be used in combination.
The copolymer of maleic anhydride and unsaturated monomer constituting the sizing agent preferably has an average molecular weight of 2,000 or more. Further, the ratio of maleic anhydride and unsaturated monomer is not particularly limited. Furthermore, in addition to the maleic anhydride copolymer, an acrylic acid copolymer or a urethane polymer may be used in combination.

As the silane coupling agent which is another component constituting the sizing agent, a silane coupling agent usually used for surface treatment of glass fibers can be used. Although not limited to the following, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) Aminosilane coupling agents such as aminopropyltrimethoxysilane and N-β (aminoethyl) aminopropyltriethoxysilane; γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycine Epoxysilane coupling agents such as sidoxypropyltriethoxysilane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrieth Methacryloxy silane coupling agent such as Shishiran; vinyltrimethoxysilane, vinyltriethoxysilane, vinylsilane coupling agents such as vinyl tris (beta-methoxyethoxy) silane; and the like.
These silane coupling agents may be used alone or in combination of two or more.
Of these, aminosilane coupling agents are particularly preferred from the viewpoint of affinity with (a-1) polyamide 66 / 6I copolymer. Among them, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ- Aminopropyltriethoxysilane is more preferred.

The ratio of the maleic anhydride copolymer and the silane coupling agent used is preferably a ratio of 0.01 to 20 parts by mass of a silane coupling agent, more preferably 100 parts by mass of the maleic anhydride copolymer. Is 5 to 20 parts by mass, more preferably 10 to 20 parts by mass.
Usually, a maleic anhydride copolymer and a silane coupling agent are mixed in an aqueous solvent and used as a sizing agent. If necessary, surfactants, lubricants, softeners, antistatic agents and the like may be added.

As mentioned above, the average fiber diameter of a monofilament (B) glass fiber is 15-18 micrometers.
(B) The average fiber diameter of monofilaments of glass fiber is 15 μm or more from the viewpoints of bundling properties and resin impregnation properties, and 18 μm or less from the viewpoint of improving mechanical strength.
Preferably, they are 16 micrometers or more and 18 micrometers or less, More preferably, they are 17 micrometers or more and 18 micrometers or less.
The average fiber diameter of the monofilament of (B) glass fiber is calculated by measuring the fiber diameter of 100 monofilaments arbitrarily using a scanning electron microscope or an optical microscope and averaging the obtained measurement values. be able to.

(B) The TEX number of the glass fiber is 3000 to 4000 (TEX) from the viewpoint of obtaining a polyamide resin composition pellet having excellent mechanical strength and excellent impregnation property and excellent operability during extrusion. 3200-3800 (TEX).
The TEX number is the mass per 1000 m of glass fiber roving, and the unit is represented by “g / 1000 m”.
(B) The TEX number of the glass fiber can be determined according to JIS R3911.
Specifically, (m / l) is calculated according to the following formula, rounded to one decimal place according to JIS Z8401, and the count (t) is obtained by multiplying this by a thousand.
t = (m / l) × 1000
t: count (TEX), m: mass of the test piece (g), l: length of the test piece (m)
Moreover, the fiber length of the (B) glass fiber in the polyamide resin composition pellet which comprises the glass long fiber reinforcement flame-retardant polyamide resin composition of this embodiment is preferable from a mechanical strength and a flame-resistant viewpoint. Is 5 to 15 mm, preferably 6 to 13 mm, more preferably 8 to 12 mm. Moreover, it is preferable that a pellet length and (B) glass fiber length in a pellet are substantially the same.
The length of the polyamide resin composition pellets constituting the long glass fiber reinforced flame retardant polyamide composition of the present embodiment is 5 to 15 mm, preferably 6 to 13 mm, more preferably 8 to 12 mm.
(B) The compounding quantity of glass fiber is (B) 50-70 mass parts with respect to said (A) polyamide resin composition 30-50 mass parts from a viewpoint of mechanical strength and the surface appearance of a molded article. , Preferably it is 50-65 mass parts, More preferably, it is 50-60 mass parts.

((C) higher fatty acid metal salt)
The long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment contains (C) a higher fatty acid metal salt (hereinafter sometimes referred to as (C) component).
Examples of the (C) higher fatty acid metal salt include, but are not limited to, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, montanic acid, melicic acid, Examples include sodium salts, lithium salts, calcium salts, magnesium salts, zinc salts, aluminum salts of higher aliphatic carboxylic acids having 9 or more carbon atoms such as oleic acid and erucic acid. From the viewpoints of properties and prevention of gas burning of molded articles, metal montanate, specifically sodium montanate and calcium montanate are preferred.
(C) The compounding amount of the higher fatty acid metal salt is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the polyamide resin composition described above, from the viewpoints of plasticizing property and mold release during molding. , Preferably it is 0.02-0.4 mass part, More preferably, it is 0.03-0.3 mass part.

((D) Colored master batch pellet)
The long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment contains (D) colored master batch pellets (hereinafter sometimes referred to as (D) component).
The (D) colored masterbatch pellet is a polyamide resin pellet containing an organic dye and / or an inorganic pigment as a colorant.
Although there is no restriction | limiting in particular about the kind and content of a coloring agent, It is preferable to select in the range which does not impair the mechanical physical property of the obtained glass fiber reinforced polyamide resin composition, and the surface appearance of a molded article.
In the case of organic dyes, it is not limited to the following, but examples include nigrosine, azine black, perinone red, perinone orange, anthraquinone blue, anthraquinone red, etc. Although not intended, for example, zinc sulfide, phthalocyanine, carbon black, titanium oxide and the like can be mentioned.
(D) Although there is no restriction | limiting in particular as a polyamide resin which is a base resin which comprises a coloring masterbatch pellet, It is the same as the (a-1) polyamide 66 / 6I copolymer of (A) polyamide resin composition. However, it is preferable from the viewpoint of plasticizing property at the time of molding and surface appearance of the molded product.

As will be described later in [Method for producing long glass fiber reinforced flame retardant polyamide resin composition], as a method for adding (C) higher fatty acid metal salt and (D) colored masterbatch pellet, resin composition From the viewpoint of improving the bite into the molding machine, stabilizing the plasticizing property, exhibiting excellent mold releasability with a small amount of addition, and obtaining a molded product with excellent surface appearance as described above (A) A method of externally adding to the polyamide resin composition pellets containing the component and the component (B) is preferred.
The method of external addition is not particularly limited. For example, the polyamide resin composition pellets are dry blended with (C) higher fatty acid metal salt and (D) colored master batch pellets, and the polyamide resin composition pellets. Examples thereof include a method of coating (C) a higher fatty acid metal salt on the surface and the surface of the (D) colored master batch pellet.
Further, (C) the higher fatty acid metal salt can be added internally as required.

(Additive)
Moreover, the glass long fiber reinforced flame-retardant polyamide resin composition of this embodiment can mix | blend various additives as desired.
Specific examples of additives include, but are not limited to, heat stabilizers for polyamides such as copper compounds and phosphorus compounds, antioxidants such as hindered phenols and hindered amines, and light such as manganese compounds. Stabilizers, nucleating agents such as talc and boron nitride, mineral fillers such as calcium carbonate, wollastonite, kaolin, calcined kaolin and mica, plasticizers, antistatic agents, thermoplastic resins other than polyamide, and the like.
These additives are added at the time of polymerization of the raw material (a-1) polyamide 66 / 6I copolymer, or (A) the polyamide resin composition or (D) described above using a single or twin screw extruder. They may be blended and melt kneaded when obtaining colored master batch pellets. In addition, when the additive is used as a master batch blend and blended in Step 4 to obtain the glass long fiber reinforced flame retardant polyamide resin composition, or when the glass long fiber reinforced flame retardant polyamide resin composition is injection molded. You may mix.

[Production method of long glass fiber reinforced flame retardant polyamide resin composition]
As a method for producing the long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment, a so-called pultrusion method can be applied.
First, (a-1) 50-90% by mass of a polyamide 66 / 6I copolymer having a sulfuric acid relative viscosity (ηr) of 1.80-2.50, (a-2) 9-35% by mass of a brominated flame retardant. And (a-3) 1-15% by mass of antimony oxide is melt-kneaded with an extruder to obtain (A) a polyamide resin composition (step 1). As the extruder for melting and kneading, a single screw or twin screw extruder can be used.
Next, the obtained (A) polyamide resin composition is impregnated in a glass fiber roving bundle (B) having a TEX number of 3000 to 4000 and an average fiber diameter of monofilaments of 15 to 18 μm in an impregnation die. An impregnated glass fiber roving bundle is obtained (step 2).
The resin temperature of the (A) polyamide resin composition at the time of impregnation is preferably the melting point of the polyamide resin + 10 ° C. to 300 ° C. from the viewpoint of excellent impregnation properties and suppressing the decomposition of the polyamide resin. A more preferable range is a melting point + 15 ° C. to 295 ° C., and further preferably a melting point + 20 ° C. to 290 ° C. Here, the resin temperature of the (A) polyamide resin composition is defined as the temperature of the barrel closest to the impregnation die of the extruder.
The heat residence time of the (A) polyamide resin composition is preferably within 7 minutes from the viewpoint of suppressing the decomposition of the (a-1) polyamide 66 / 6I copolymer and (a-2) brominated flame retardant. . A more preferable range is within 6 minutes, and a further preferable range is within 5 minutes.
The (A) heat residence time of the polyamide resin composition is defined as the heat residence time in an impregnation die in which (B) the glass fiber roving bundle is impregnated with the (A) polyamide resin composition. ).

Next, the obtained resin-impregnated glass fiber roving bundle is continuously drawn from the spinning nozzle to obtain a strand. The obtained strands are pelletized to obtain pellets having a length of 5 to 15 mm containing glass fibers having substantially the same length as the pellets (step 3).
Next, (C) higher fatty acid metal salt and (D) colored master batch pellet are externally added to the pellet (step 4).

  In the above (Step 1) to (Step 4), when the amount of the component (A) to the component (D) is adjusted and the total amount of the component (A) and the component (B) is 100 parts by mass, (A) 30 to 50 parts by mass, (B) 50 to 70 parts by mass, (C) 0.01 to 0.5 parts by mass, and (D) 1 to 10 parts by mass of a glass long fiber reinforced flame retardant polyamide resin composition. obtain.

[Use of long glass fiber reinforced flame retardant polyamide resin composition]
The long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment has stable flame retardancy, high impact resistance, and excellent appearance of a molded product. Accordingly, the long glass fiber reinforced flame retardant polyamide resin composition can be suitably used in electromagnetic switch parts and breaker parts.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

  Various measurement methods for the characteristics of raw materials, glass long fiber reinforced flame retardant polyamide resin compositions and molded bodies used in Examples and Comparative Examples are shown below.

〔raw materials〕
((A-1) polyamide 66 / 6I copolymer)
(A-1) The following (a-1-1) to (a-1-3) were used as the polyamide 66 / 6I copolymer.
(A-1-1): Polyamide 66 / 6I (66 component: 85% by mass, 6I component: 15% by mass, sulfuric acid relative viscosity: 2.3, melting point: 245 ° C.)
Production method of (a-1-1) 1.7 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.3 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 3 g of acetic acid, and 2.0 kg of pure water Were placed in a 5 liter autoclave and the inside of the autoclave was sufficiently purged with nitrogen while stirring well. The autoclave temperature was raised from room temperature to 220 ° C. over 1 hour while stirring was continued. Thereafter, the temperature inside the autoclave was raised to 260 ° C. over 2 hours while removing water from the reaction system so that the internal pressure of the autoclave became 1.8 MPa. Thereafter, the heating was stopped, the autoclave was sealed, and the mixture was cooled to room temperature over 8 hours to obtain about 1.6 kg of polyamide 66 / 6I copolymer. The obtained polyamide 66 / 6I copolymer was pulverized and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream using a 10 liter evaporator to obtain (a-1-1). The sulfuric acid relative viscosity η _r increased from 1.5 to 2.3 by solid phase polymerization.
In Tables 1 and 2, the relative viscosity of sulfuric acid is shown in parentheses.

(A-1-2): Polyamide 66 / 6I (66 component: 85% by mass, 6I component: 15% by mass, sulfuric acid relative viscosity: 2.6, melting point: 245 ° C.)
Production method of (a-1-2) Except that the time for solid phase polymerization was changed to 14 hours, the production method was the same as that of (a-1-1), and (a-1-2) was produced. Obtained.
Sulfuric acid relative viscosity is compliant with JIS K6810, and measure in accordance with this scheme.
The sulfuric acid relative viscosity (ηr) was measured using an Ostwald viscometer (a-1) the number of seconds of dripping of the polyamide resin solution and the number of seconds of dripping of the sulfuric acid solution under a temperature condition of 25 ° C., and the measured values were used. The following formula was used.
In the following formula, the polyamide resin is (a-1) a polyamide 66 / 6I copolymer.
Sulfuric acid relative viscosity (ηr) = (Polyamide resin solution dropping seconds) / (Sulfuric acid solution dropping seconds)
Here, the polyamide resin solution in the formula is obtained by dissolving the polyamide resin in a 96% sulfuric acid solution to a concentration of 0.01 g / mL.
Melting point, using a Perkin Elmer DSC7, and held 5 minutes at 80 ° C., 20 ° C.
The temperature is once raised to 300 ° C. at a rate of / min, then lowered to 40 ° C. at 20 ° C./min,
The temperature was measured at a rate of ° C / min. The endothermic peak based on melting at this time was defined as the melting point.

(A-1-3): Polyamide 66 / 6I (66 component: 85% by mass, 6I component: 15% by mass, sulfuric acid relative viscosity: 1.5, melting point: 245 ° C.)
Production method of (a-1-3) Except that solid phase polymerization was not performed, the production method was the same as that of (a-1-1) to obtain (a-1-3).

  (A-1-4): Polyamide 66 (trade name: Leona 1200S011, manufactured by Asahi Kasei Chemicals, sulfuric acid relative viscosity: 2.4, melting point: 260 ° C.)

((A-2) Brominated flame retardant)
(A-2) The following (a-2-1) was used as a brominated flame retardant.
(A-2-1): Brominated polystyrene (trade name: SAYTEX HP-3010, manufactured by Albemarle Japan Ltd.)

((A-3) antimony oxide)
(A-3): The following (a-3-1) was used as a flame retardant aid.
(A-3-1): Antimony trioxide (trade name: AN-800 (T), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

((B) Glass fiber)
As the glass fiber, the following (b-1) to (b-3) were used.
(B-1): Glass fiber roving (trade name: ER4301H, manufactured by Chongqing International Composite Material Co., Ltd., monofilament average fiber diameter: 17 μm, TEX number: 1200 TEX)
(B-2): Glass fiber roving (trade name: T-448N, manufactured by Nippon Electric Glass Co., Ltd., monofilament average fiber diameter: 17 μm, TEX number: 2400 TEX)
(B-3): Glass fiber roving (average filament diameter of monofilament: 10 μm, TEX number: 3600 TEX)
The average fiber diameter of the monofilament was calculated by arbitrarily measuring the fiber diameter of 100 monofilaments using a scanning electron microscope and averaging the obtained measurement values.
The number of TEX was obtained in accordance with JIS R3911.
Specifically, (m / l) was calculated according to the following formula, rounded to one digit after the decimal point according to JIS Z8401, and the count (t) was obtained by multiplying this by a thousand.
t = (m / l) × 1000
t: count (TEX), m: mass of the test piece (g), l: length of the test piece (m)

((C) higher fatty acid metal salt)
(C): The following (c-1) was used as a higher fatty acid metal salt.
(C-1): Calcium montanate (trade name: Licomont CaV 102, manufactured by Clariant Japan Co., Ltd.)

((D) Colored master batch pellet)
(D): The following (d-1) was used as a colored master batch pellet.
(D-1): Black colored MB (trade name: NYLONBLACK 7698, manufactured by Dainippon Ink & Chemicals, Inc.)

[Glass long fiber reinforced flame retardant polyamide resin composition, various measurement methods for the characteristics of the molded product]
(Bending elastic modulus, bending strength, and Charpy impact strength)
Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is the melting point of polyamide resin + 50 ° C., the mold temperature is 80 ° C., the injection pressure is 65 MPa, the injection time is 5 seconds, A multipurpose test piece A type according to ISO 3167 was molded under the molding conditions of cooling time of 25 seconds and screw rotation speed of 200 rpm.
Further, the multi-purpose test piece A type was cut into a bending test specimen and a notched Charpy impact strength test specimen.
Using the test piece for bending test, in accordance with ISO 178, with an autograph (manufactured by Shimadzu Corporation: AG-5000D type) under conditions of a crosshead speed of 5 mm / min and a span of 64 mm, the bending elastic modulus and bending strength Was measured.
Using the notched Charpy impact strength test specimen, according to ISO 179, Charpy impact strength test equipment (Toyo Seiki Co., Ltd .: DG-C (A, B) Charpy method) was used. The strength was measured.

[Flame retardance test]
Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is the melting point of polyamide resin + 50 ° C., the mold temperature is 80 ° C., the injection pressure is 65 MPa, the injection time is 5 seconds, A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 0.80 mm was molded from the obtained pellets under the molding conditions of a cooling time of 25 seconds and a screw speed of 200 rpm.
The flammability of the test piece was measured according to the method of UL94 (a standard defined by Under Writers Laboratories Inc., USA).

[Flammability test]
Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is the melting point of polyamide resin + 50 ° C., the mold temperature is 80 ° C., the injection pressure is 65 MPa, the injection time is 5 seconds, A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 2.0 mm was molded under the molding conditions of a cooling time of 25 seconds and a screw rotation speed of 200 rpm.
The flammability of the test piece was measured according to the method of GWFI (standard defined in IEC60695-2-12).

[Evaluation of plasticizing properties (Evaluation of variation in plasticizing time during injection molding)]
Using a PS-40E5A injection molding machine manufactured by Nissei Resin Co., Ltd., a strip of 200 was formed under constant conditions of cylinder temperature 290 ° C., mold temperature 80 ° C., injection time 10 seconds, cooling time 10 seconds, rest time 0 seconds, injection pressure 55 MPa. The plasticizing time at the time of continuous shot molding was measured, and the variation time was determined.
Regarding the variation time, the width of “maximum plasticization time” and “minimum plasticization time” was measured and expressed by numerical values with ± in Tables 1 and 2, and the smaller the absolute value, the better the evaluation. did.

[Appearance of molded product (glass fiber lump, gas burn)]
Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is the melting point of polyamide resin + 50 ° C., the mold temperature is 80 ° C., the injection pressure is 50 MPa, the injection time is 5 seconds, A flat plate (15 cm × 15 cm, thickness 4 mm) was injection molded under the molding conditions of a cooling time of 25 seconds and a screw rotation speed of 200 rpm, and 10 obtained flat plate plates were visually observed.
When the glass fiber lump was not observed on the surface of the molded product, it was judged as “good”, and when the glass fiber lump was observed even at one place, it was judged as “x”.
In addition, when no discoloration due to gas burn was observed on the surface of the molded product, it was judged as ◯ when no discoloration due to gas burn was observed even at one location.
As the evaluation of the appearance of the molded product, when both of the above two evaluations were “◯”, it was judged as good: ◯, and when either one was “x”, it was judged as defective: x.

A long glass fiber reinforced flame retardant polyamide resin composition was produced as follows.
[Examples 1 to 4]
From the top feed port in a twin screw extruder (trade name: ZSK25, manufactured by Coperion), the ratio shown in Table 1 below is (a-1-1) polyamide 66 / 6I, (a-2-1) brominated polystyrene. And (a-3-1) diantimony trioxide was supplied and melt-kneaded at a cylinder set temperature of the melting point of the polyamide resin + 40 ° C. and a screw rotation speed of 300 rpm to obtain a polyamide resin composition (A).
The obtained (A) polyamide resin composition was supplied to an impregnation die (volume: 375 cc) provided with a resin impregnation roller in a long fiber reinforced resin production apparatus (KOSLFP-212, manufactured by Kobe Steel, Ltd.).
On the other hand, three (b-1) glass fiber rovings were used as (B) glass fiber roving bundles (TEX number: 3600 (TEX)) from the roving table at the ratio shown in Table 1 below. (A) A polyamide resin composition is introduced into a cross head of an impregnation die filled with a polyamide resin composition, and (B) a glass fiber roving bundle is impregnated with (A) the polyamide resin composition in the impregnation die. An impregnated glass fiber roving bundle was obtained.
The obtained polyamide resin composition-impregnated glass fiber roving bundle was continuously withdrawn from the spinning nozzle (diameter 2.2 mm) to obtain one strand.
The strand was cooled and solidified in a water-cooled bath. The cooled and solidified strand was made into a polyamide resin composition pellet (length 10 mm, diameter 2.2 mm) with a pelletizer.
The glass fiber length in the polyamide resin composition pellet was 10 mm.
Thereafter, (c-1) calcium montanate and (d-1) black-colored MB were externally added to the obtained pellets at a ratio shown in Table 1 below, followed by dry blending, whereby glass long fiber reinforced flame retardancy. A polyamide resin composition was obtained. The evaluation results are shown in Table 1.

[Comparative Example 1]
As (a-1), (a-1-2) polyamide 66 / 6I was used. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 1 shows the evaluation results.
The long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 1 is more impregnable into the glass fiber roving bundle of (A) the polyamide resin composition than that obtained in Example 1. Unfortunately, since the resulting pellets had a lot of fluff, the plasticizing property at the time of molding was deteriorated, and the impact strength of the obtained molded product was low, indicating that the surface appearance of the molded product was inferior.

[Comparative Example 2]
As (a-1), (a-1-3) polyamide 66 / 6I was used. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 1 shows the evaluation results.
It was found that the long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 2 was inferior in mechanical strength as compared with that obtained in Example 1.

[Comparative Example 3]
(A-1-4) Polyamide 66 was used as (a-1). The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 1 shows the evaluation results.
It was found that the long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 3 was inferior to the surface appearance of the molded product as compared with that obtained in Example 1.

[Comparative Example 4]
One (b-2) glass fiber roving was introduced into the crosshead of the impregnation die. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 1 shows the evaluation results.
The long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 4 is not only inferior in mechanical strength to that obtained in Example 1, but also (A) the polyamide resin composition. It was found that the impregnation property of the glass fiber roving bundle was poor and the pellets obtained had a lot of fluffing, so that the plasticizing property at the time of molding was poor and the surface appearance of the molded product was inferior.

[Comparative Example 5]
(B) Glass fiber roving was used as (B) glass fiber. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 1 shows the evaluation results.
It was found that the long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 5 was inferior in mechanical strength of the molded product as compared with that obtained in Example 1.

[Comparative Example 6]
The pellet length was cut to 3 mm with a pelletizer. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 1 shows the evaluation results.
It was found that the long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 6 was significantly inferior in mechanical strength of the molded product as compared with that obtained in Example 1.

[Comparative Examples 7 to 10]
As in Examples 1 to 4, (A) polyamide resin composition and (B) glass fiber were used in the proportions shown in Table 2. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 2 shows the evaluation results.
It was found that the long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 7 was inferior in flame retardancy as compared with that obtained in Example 1.
The long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 8 is inferior to the one obtained in Example 1 in mechanical strength, particularly impact resistance, and further molded. The product appearance was found to be inferior.
It was found that the long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 9 was significantly inferior in mechanical strength of the molded product as compared with that obtained in Example 1.
The long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 10 was severely cracked and fuzzed, and could not be molded because the pellets did not bite during molding.

[Comparative Example 11]
(C) A higher fatty acid metal salt was not blended. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 2 shows the evaluation results.
The long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 11 is unstable in plasticizing property at the time of molding as compared with that obtained in Example 1, and the molded article surface appearance is improved. I found it inferior.

[Comparative Example 12]
(D) A colored master batch pellet was not blended. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 2 shows the evaluation results.
The glass long fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 12 is significantly unstable in plasticizing property and inferior in the surface appearance of the molded product as compared with that obtained in Example 1. I understood.

[Comparative Example 13]
(C) 1 part by mass of a higher fatty acid metal salt was blended. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 2 shows the evaluation results.
The glass long fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 13 is unstable in plasticizing property at the time of molding as compared with that obtained in Example 1, and the surface appearance of the molded product is improved. Not only was it inferior, it was also found that the flame retardancy was significantly inferior.

[Comparative Example 14]
(D) 15 parts by mass of a colored master batch pellet was blended. The other conditions were the same as in Example 1 to obtain a glass long fiber reinforced flame retardant polyamide resin composition. Table 2 shows the evaluation results.
The long glass fiber reinforced flame retardant polyamide resin composition obtained in Comparative Example 14 is not only inferior to the mechanical strength of the molded product as compared with that obtained in Example 1, but also has remarkable flame retardancy. I found it inferior.

  The long glass fiber reinforced flame retardant polyamide resin composition of the present embodiment has industrial applicability as a material for parts such as parts in the electric / electronic field and electrical parts in the automobile field.

Claims (3)

Polyamide resin composition pellets,
(A): (a-1) 50 to 90% by mass of a polyamide 66 / 6I copolymer having a sulfuric acid relative viscosity (ηr) of 1.80 to 2.50 measured according to JIS K6810 , (a-2 30) to 50 parts by mass of a polyamide resin composition containing 9 to 35% by mass of a brominated flame retardant and (a-3) 1 to 15% by mass of antimony oxide;
(B): TEX number is 3000 to 4000 (TEX), monofilament average fiber diameter is 1
50 to 70 parts by mass of glass fiber having a length of 5 to 18 μm and a length of 5 to 15 mm in the polyamide resin composition pellets;
And 100 parts by mass of a polyamide resin composition pellet having a length of 5 to 15 mm,
(C): 0.01 to 0.5 parts by mass of a higher fatty acid metal salt;
(D): 1 to 10 parts by mass of colored master batch pellets;
including,
A long glass fiber reinforced flame retardant polyamide resin composition. The glass fiber reinforced fiber according to claim 1, wherein the proportion of 66 components of the (a-1) polyamide 66 / 6I copolymer is 60 to 90 mass% and the proportion of 6I components is 10 to 40 mass%. Flame retardant polyamide resin composition. A molded product obtained by molding the long glass fiber reinforced flame-retardant polyamide resin composition according to claim 1 or 2.