JP2009120701A - Fire-resistant polyamide resin composition reinforced by glass fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition with extremely high rigidity, extremely high flame-retardancy and excellent moldability, with not generating a halogen gas with a high corrosion property or the like during burning, and in particular, to provide a fire-resistant reinforced polyamide resin composition suitably used for parts in electric and electronic fields, part materials of electric equipment parts or the like in the automobile field and parts of household electric appliances, and the like. <P>SOLUTION: The polyamide resin composition reinforced by a fire-resistant glass fiber comprises (A) 20-60 mass% of a polyamide resin, (B) 40-70 mass% of an inorganic filler and (C) 5-20 mass% of a flame-retardant not containing a halogen element, and in the resin composition, the flame-retardant is a specific phosphinate and/or diphosphinate and 0.2&le;(C)/(A)&le;0.4, wherein, the flame-retardant glass fiber reinforced polyamide resin composition contains (D) 0.05-2 pts.mass of a silicone oil based on 100 pts.mass of the resin composition, and 0.001&le;(D)/(A)&le;0.1. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is a resin composition having very high rigidity, extremely high flame retardancy, no generation of highly corrosive halogen gas and the like, and excellent moldability. In particular, the present invention relates to a flame-retardant reinforced polyamide resin composition that is suitably used for parts in electrical and electronic fields, parts materials such as electrical parts in automobiles, and parts for household electrical appliances.

  Polyamide resins have excellent mechanical properties and heat resistance, and are therefore used in a wide variety of fields such as electric / electronics, automobiles, machinery, and building materials. Recently, resin substitution by metal substitution has progressed, and resin has required strength and rigidity equivalent to metal. In particular, advanced flame retardancy is required for electrical components such as connectors and household appliances such as notebook computers. In order to make a resin flame-retardant, generally, a method of adding a halogen-based flame retardant or a triazine-based flame retardant or a method of depositing Mg on a resin are taken. However, halogen flame retardants are said to have adverse effects on the environment and the human body, such as corrosive halogen gases and harmful substances generated during combustion, and there is a movement to regulate the use of halogen flame retardants, and Mg deposition is also costly High and undesirable.

  For this reason, halogen-free triazine flame retardants have attracted attention and many studies have been made. For example, a technique using melamine as a flame retardant (patent document 1), a technique using cyanuric acid (patent document 2), and a technique using melamine cyanurate (patent document 3) are well known. With these technologies, flame retardant that meets UL94 V-0 standard can be achieved with a thickness of 1/32 inch in a system that does not contain reinforcement, but when reinforced with glass fiber, etc., a large amount of flame retardant is added. Even so, there is a problem in that it ignites cotton and does not conform to the UL94 V-0 standard.

  On the other hand, flame retardant technology (Patent Document 9) is proposed in which melamine phosphate, melamine pyrophosphate, or melamine polyphosphate, which are intumescent flame retardants, is used for glass fiber reinforced polyamide resin. In order to satisfy UL94 V-0 standard for inch thickness, it is necessary to add a lot of these melamine phosphate flame retardants, so electrical properties such as toughness, mechanical properties and tracking resistance In some cases, it was lowered and was not satisfactory in practical use.

Furthermore, a technique (for example, Patent Document 5) that combines a phosphinate and (a reaction product of melamine and phosphoric acid), and a technique that combines a phosphinic acid salt (a reaction product of melamine and phosphoric acid) and a metal compound. (For example, Patent Document 6 and Patent Document 7) have been proposed, and it is known that a 1/16 inch molded product satisfies the flame retardancy standard UL94V-0 standard. With this technology, due to the synergistic effect of two or more flame retardants, it is possible to reduce the amount of the flame retardant and improve mechanical properties (particularly toughness such as bending deflection) and electrical properties (tracking resistance). . However, when the inorganic filler is contained in an amount of 40% or more, the operability during extrusion is greatly reduced. Furthermore, since the fatty acid metal salt with good flammability is contained for improving the fluidity and mold releasability at the time of molding, it was not satisfactory because the flame retardancy remained uneasy.
Japanese Examined Patent Publication No. 47-1714 JP 50-105744 A JP-A-53-31759 Japanese National Patent Publication No. 10-505875 JP 2004-263188 A Japanese Patent Application No. 2005-209678 Japanese Patent Application No. 2005-209679

  The present invention provides a flame retardant reinforced polyamide resin composition that is extremely rigid, extremely flame retardant, does not generate corrosive halogen gas during combustion, and has excellent moldability. Objective.

  As a result of diligent investigation to solve the above-mentioned problems, the present inventor achieved the above object by blending a phosphinate and a silicone oil in a specific ratio in a system combining a polyamide resin and an inorganic filler. The inventors have found that this can be solved and have reached the present invention.

  That is, the gist of the present invention is as follows.

  (1) (A) Polyamide resin 20 to 60% by mass, (B) Inorganic filler 40 to 70% by mass, (C) 5-20% by mass of a flame retardant containing no halogen element. I) and / or diphosphinic acid salt represented by formula (II), wherein 0.2 ≦ (C) / (A) ≦ 0.4, (A), When the resin composition obtained by blending (B) and (C) is 100 parts by mass, (D) 0.05 to 2 parts by mass of silicone oil is included and 0.001 ≦ (D) / (A) ≦ 0.1 A flame retardant glass fiber reinforced polyamide resin composition.

(Wherein R ₁ , R ₄ and R ₂ , R ₅ are each linear or branched C ₁ -C ₁₆ alkyl, preferably C ₁ -C ₈ alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-octyl, and phenyl, and R ₁ and R ₂ and R ₄ and R ₅ may form a ring with each other, and R ₃ is linear or branched. C ₁ -C ₁₀ alkylene, in particular methylene, ethylene, n- propylene, isopropylene, isopropylidene, n- butylene, tert- butylene, n- pentylene, n- octylene, n- dodecylene; arylene, in particular phenylene, naphthylene, alkyl Arylene, especially methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene; arylalkylene, especially phenylmethylene, phenylethylene , Phenylpropylene, phenylbutylene, M is calcium or aluminum ion, m is 2 or 3, n is 1 or 3, and x is 1 or 2. mx = 2n in formula (II) .)

  (2) The flame retardant glass fiber reinforced polyamide resin composition according to (1), wherein the inorganic filler is a flat glass fiber having a flat cross section having a major axis / minor axis ratio of 1.5 to 10.

(3) The silicone oil is a methylphenyl silicone oil having a specific gravity (25 ° C.) of 1.03 to 1.06 and a kinematic viscosity (25 ° C.) of 100 to 300 mm ² / s (1) or The flame retardant glass fiber reinforced polyamide resin composition of (2).

  (4) A molded product having a thickness of 1/32 inch obtained by molding a flame retardant glass fiber reinforced polyamide resin composition is V-0 by a flammability test according to safety standard UL94 (1 ) To (3), the flame retardant glass fiber reinforced polyamide resin composition.

  According to the present invention, it is possible to provide a resin composition having very high rigidity, extremely high flame retardancy, no generation of highly corrosive halogen gas and the like, and excellent moldability. -Since it can be suitably used for parts in electronic fields, parts materials such as electrical parts in automobiles, parts for household electrical appliances, etc., the industrial utility value is extremely high.

  The present invention will be specifically described below.

  The resin of the polyamide resin (A) in the present invention is a polymer having an amide bond in the main chain, the main raw material of which is aminocarboxylic acid, lactam or diamine and dicarboxylic acid (including a pair of salts thereof). . Preferred examples of the polyamide resin include polycapramide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polycoupler / polyhexamethylene adipamide copolymer (nylon 6/66) ), Polyundecamide (nylon 11), polycapramide / polyundecamide copolymer (nylon 6/11), polydodecamide (nylon 12), polycoupler / polydodecamide copolymer (nylon 6/12), polyhexamethylene sebamide (nylon 610) ), Polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene terephthalamide / Poly Xamethylene isophthalamide copolymer (nylon 6T / 6I), polycapramide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polycapramide / polyhexamethylene isophthalamide copolymer (nylon 6 / 6I), polyhexamethylene adipamide / poly Hexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polytrimethylhexamethylene terephthalamide (nylon TMDT), polybis (4-aminocyclohexyl) Methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methandecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene tele Examples thereof include phthalamide (nylon 11T) and mixtures or copolymers thereof. Of these, nylon 6, nylon 66, and mixtures thereof are particularly preferred.

  (A) The compounding quantity of a polyamide resin needs to be 20-60 mass%. If it is less than 20% by mass, the molding processability and mechanical properties are deteriorated, and if it exceeds 60% by mass, the rigidity is inferior. Further, the relative viscosity (measured under the conditions of 96 mass% concentrated sulfuric acid as a solvent, temperature 25 ° C., concentration 1 g / dl) is in the range of 1.7 to 2.7, and more preferably in the range of 1.9 to 2.6. If the relative viscosity is less than 1.7, the mechanical properties may deteriorate, and if it exceeds 2.7, gas and decomposition products are likely to be generated during melt-kneading, and flame retardancy may not be achieved. .

  (B) Inorganic filler in the present invention includes glass fiber, carbon fiber, potassium titanate fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, basalt fiber, mica, talc, silica, calcium carbonate , Kaolin, calcined kaolin, wollastonite, glass beads, glass flakes, fibrous oxides such as glass flakes, titanium oxide, etc., and inorganic reinforcing materials in the form of needles or needles. Two or more of these reinforcing materials may be used in combination. In particular, glass fiber, wollastonite, talc, calcined kaolin and mica are preferably used, and among these, glass fiber is more preferable.

  Further, the glass fiber can be selected from long fiber type roving, short fiber type chopped strand, milled fiber and the like. It is preferable to use a glass fiber that has been surface-treated for polyamide. Furthermore, the cross section of the glass fiber is not limited to circular, flat gourd, eyebrows, oval, ellipse, rectangle or similar products, but the warp peculiar to glass fiber compounded polyamide is not limited. In order to reduce the ratio, a flat fiber having a major axis / minor axis ratio of 1.5 to 10 is used, more preferably 2.0 to 6.0. When the ratio of major axis / minor axis is 1.5 or less, the effect of flattening the cross section is small, and when the ratio is 10 or more, it is difficult to produce the glass fiber itself.

  (B) The compounding quantity of an inorganic filler is 40-70 mass%, Preferably it is 40-60 mass%. If it is less than 40% by mass, the strength, rigidity and heat resistance are not satisfied, and if it exceeds 70% by mass, melt kneading workability and molding processability are deteriorated.

  The phosphinic acid salt in the present invention means phosphinic acid and diphosphinic acid and salts of their polymers. Phosphinate is produced in an aqueous solution using phosphinic acid and metal carbonate, metal hydroxide or metal oxide and exists essentially as a monomer, but depending on the reaction conditions, the degree of condensation is 1 to It may also exist in the form of 3 polymeric phosphinates. In the present invention, preferred phosphinic acid salts are phosphinic acid salts and diphosphinic acid salts, and phosphinic acid salts, diphosphinic acid salts, and mixtures thereof are particularly preferred from the viewpoint of dispersibility in kneading with a resin. preferable.

  Phosphinic acid suitable as a component of the phosphinic acid salt includes dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethyl Phosphinic acid), methylphenylphosphinic acid and diphenylphosphinic acid. In addition, examples of the metal component include calcium carbonate, magnesium ion, aluminum ion, and / or metal carbonate, metal hydroxide, or metal oxide containing zinc ion.

  Phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, diethyl Calcium phosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinate, methyl-n- Examples include zinc propylphosphinate.

  Also, methanedi (methylphosphinic acid) calcium, methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1 , 4- (dimethylphosphinic acid) magnesium, benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, methylphenyl Examples include aluminum phosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. In particular, aluminum diethylphosphinate and zinc diethylphosphinate are preferable from the viewpoint of flame retardancy and electrical characteristics.

  The blending amount of the flame retardant not containing (C) halogen element is 5 to 20% by mass, and the ratio with (A) polyamide must be 0.2 ≦ (C) / (A) ≦ 0.4, preferably 0.25 ≦ (C) / (A) ≦ 0.35. If 0.2> (C) / (A), flame retardancy cannot be achieved, and if (C) / (A)> 0.4, the operability during extrusion, mechanical strength and mold Since contamination occurs, it is not preferable.

  The (D) silicone oil used in the present invention is an organosilicon compound having a siloxane bond as a skeleton and an organic group or the like directly bonded to the silicon. As an organic group directly bonded to silicon, a methyl group, an ethyl group, a phenyl group, a vinyl group, a trifluoropropyl group, and a combination thereof are known, but a known silicone oil having these is used without any particular limitation. it can. Some organic groups were substituted with substituents having epoxy groups, amino groups, polyether groups, carboxyl groups, mercapto groups, ester groups, chloroalkyl groups, alkyl groups having 3 or more carbon atoms, hydroxyl groups, and the like. Silicone oil can also be used.

  Specific examples of the silicone oil of the present invention include dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil, polyether-modified silicone oil, aliphatic ester-modified silicone oil, amino-modified silicone oil, and carboxylic acid-modified. Examples thereof include oily silicones such as silicone oil, carbinol-modified silicone oil, epoxy-modified silicone oil, and mercapto-modified silicone oil.

Among them, methylphenyl silicone oil is one in which the heat resistance of dimethyl silicone oil has been improved by introducing a phenyl group, and can be used for kneading with a resin or a flame retardant while appropriately suppressing an increase in kinematic viscosity, It can be used suitably. Furthermore, it is most preferable to use methylphenyl silicone oil having a specific gravity (25 ° C.) of 1.03 to 1.06 and a kinematic viscosity (25 ° C.) of 100 to 300 mm ² / s. When the specific gravity is less than 1.03, there is a concern of bleeding out of the silicone oil when the resin composition is formed into a molded product. When the specific gravity exceeds 1.06, the silicone is kneaded with a resin or a flame retardant. Oil dispersibility becomes insufficient. When the kinematic viscosity is less than 100 mm ² / s, the introduction of phenyl groups into the silicone oil skeleton is insufficient and the heat resistance is poor, and when the kinematic viscosity exceeds 300 mm ² / s, the introduction of phenyl groups is not Dispersibility of silicone oil becomes insufficient in kneading with a sufficient resin or flame retardant.

  The (D) silicone oil of the present invention can be used alone or in combination of two or more. The blending amount is 0.05 to 2.0 parts by weight with respect to 100 parts by weight of a resin composition obtained by blending (A) a polyamide resin, (B) an inorganic filler, and (C) a flame retardant containing no halogen element. Preferably it is 0.1-1.5 weight part, More preferably, it is 0.1-1 weight part. If the blending amount is less than 0.05 parts by weight, a sufficient effect of improving the releasability cannot be obtained. When the amount exceeds 2.0 parts by weight, the amount of mold deposit (MD) increases and the number of times of mold maintenance increases, so that the molding processability of the resin composition is inferior, the amount of gas generation increases, and the appearance deteriorates. Furthermore, the adhesion of the coating film also decreases. Further, it is necessary that 0.001 ≦ (D) / (A) ≦ 0.1 for blending (A) polyamide resin and (D) silicone oil. If 0.001> (D) / (A), the releasability is insufficient, and if (D) / (A)> 0.1, bleeding out tends to occur.

  Silicone oil is mainly effective in improving fluidity and releasability. In order to improve fluidity and releasability, an aliphatic amine, a fatty acid metal salt, an ethylene bisamide compound, and an aliphatic amide are generally added. However, since the flammability is increased, the flame retardant effect is not exhibited. Therefore, it is necessary to use silicone oil for the flame retardant reinforced polyamide resin composition according to the present invention.

  Furthermore, since silicone oil also exhibits a flame retardant effect, it is possible to achieve both high flame retardancy and good moldability by using (C) a flame retardant that does not contain a halogen element and (D) silicone oil. Since the amount of flame retardant added can also be reduced, it is possible to prevent deterioration in operability during extrusion, mechanical strength, and mold contamination, which are likely to occur when a large amount of flame retardant is blended.

  In the flame-retardant-reinforced polyamide resin composition of the present invention, other components such as colorants such as pigments and dyes, heat stabilizers, weather resistance improvers, nucleating agents, plasticizers, and the like, within a range that does not impair the purpose. Additives such as mold release agents and antistatic agents, and other resin polymers can be added.

  The method for producing the flame-retardant polyamide resin composition of the present invention is not particularly limited, but it is preferably melt-kneaded at a temperature of 200 to 350 ° C. using a twin-screw extruder, and has flame retardancy and mechanical properties. In order to achieve both, it is preferable to add the inorganic filler and degas it under reduced pressure after sufficiently melting and mixing raw materials other than the inorganic filler.

The best manufacturing method is (1) blending silicone oil with polyamide resin pellets, (2)
Next, the flame retardant is blended and fed to the extruder. By adhering silicone oil to the surface of the polyamide resin pellets before blending the flame retardant, the resin pellet surface is made sticky, making it easy to attach the flame retardant as a powder to the pellet, In addition to improving the familiarity, it can be uniformly dispersed in the resin. Therefore, it is preferable that the viscosity of the silicone oil is high. If the blending order is changed, the flame retardant tends to aggregate and the dispersibility of the silicone oil also deteriorates. This is not preferable, and the operability at the time of melt-kneading is deteriorated, and the releasability at the time of molding may be lowered. Moreover, sufficient flame retardance cannot be expressed.

  The composition of the present invention can be produced by various methods such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs, switches, etc. by various known methods such as injection molding, extrusion molding and blow molding. Etc.

Next, the present invention will be described more specifically with reference to examples. The materials used and the evaluation methods in the examples and comparative examples are as follows.
(1) Materials used (A) Polyamide resin (A) -1: Polyamide 66 24AD1 manufactured by Rhodia
(A) -2: Polyamide 6 Unitika 1015
(B) Inorganic filler (B) -1: Glass fiber CS03JAFT692 (average fiber diameter 10 μm) manufactured by Asahi Fiber Glass Co., Ltd.
(B) -2: Glass fiber CSG3PA820S manufactured by Nittobo Co., Ltd. (flat glass fiber having an oval cross section with a major / minor diameter ratio of 4)
(B) -3: Wollastonite Nyglos8 made by Nyco
(C) Flame retardant (C) -1: Phosphinate Aluminum diethylphosphinate (abbreviated as DEPAL)
(C) -2: Melamine polyphosphate Melapur200 / 70 manufactured by Ciba Specialty Chemicals (abbreviated as PMP)
(C) -3: Melamine cyanurate MC25 manufactured by Ciba Specialty Chemicals (abbreviated as MC)
(D) Silicone oil (D) -1: Methylphenyl silicone oil GE Toshiba Silicones Co., Ltd. TSF4300 (specific gravity 1.05, kinematic viscosity 140 mm ² / s)
(D) -2: Dimethyl silicone oil GE TOSHIBA Silicone TSF400 (specific gravity 0.951, kinematic viscosity 3.0 mm ² / s)
(D) -3: Polyether-modified silicone oil GE Toshiba Silicones TSF4446 (specific gravity 1.02, kinematic viscosity 1400 mm ² / s)
(2) Evaluation method
a) Operability at the time of melt-kneading Example and comparative example when producing 10kg under conditions of cylinder temperature 280 ℃, screw rotation speed 200rpm, discharge rate 35kg / h using twin screw extruder (TEM37 manufactured by Toshiba Machine) The state of the strand was confirmed visually. When the strand is not broken at the time of operation, the strand shape is stable ◎, the strand is not broken at all, the strand shape is disjoint and unstable, ○, the one that has broken even once is ×, the strand Were evaluated as having good operability and were deemed acceptable.
b) Bending strength and flexural modulus Using a FANUC injection molding machine (α-100iA), test pieces were molded at a resin temperature of 280 ° C and a mold temperature of 100 ° C, and measured according to ASTM D790. A bending strength of 200 MPa or more and a bending elastic modulus of 12 GPa or more were accepted.
c) Flame retardancy Using a FANUC injection molding machine (α-100iA), test specimens were molded at a resin temperature of 280 ° C and a mold temperature of 100 ° C, and UL94 (standard established by Under Writers Laboratories Inc., USA) Measured according to the method. The thickness of the test piece was 1/32 inch (about 0.8 mm). V-0 is desirable.
d) Moldability Shallow cup shape (wall thickness 1.5mm, outer diameter 40mm, depth) with a FANUC injection molding machine (α-100iA) at a resin temperature of 280 ° C, mold temperature of 100 ° C, and a cycle of 25 seconds. 30 mm) was used to visually observe the molding state when the molded product was continuously shot for 30 shots and the presence or absence of a protruding pin mark on the molded product. ◎ can be molded without any problem and no protruding pin mark is observed on the molded product, ◎ can be molded without any problem, ○ is slightly protruding pin mark is recognized, when the mold is opened, the molded product is on the fixed side of the mold The case where no marks remain and hinders continuous molding, or the case where the trace of the protruding pin is recognized even if molding can be performed without any problem, was marked with x. ◎ and ○ were accepted.

Example 1
When polyamide resin (A) -1 is 45% by mass, inorganic filler (B) -1 is 55% by mass and 100 parts by mass, flame retardant (C) -1 is 13 parts by mass, silicone oil (D)- Using a twin-screw extruder (TEM37, manufactured by Toshiba Machine), 1 is 0.8 parts by mass, melt-kneaded under the conditions of a cylinder set temperature of 280 ° C, screw rotation of 200 rpm, and a discharge rate of 35 kg / h, and then taken out into a strand. After cooling, the mixture was granulated with a cutter to obtain polyamide resin composition pellets. At that time, (1) a polyamide resin and silicone oil were blended, (2) a blend of a flame retardant was then introduced from the base, and glass fibers were fed from the side feed to the extruder. Various characteristics of the obtained pellets were evaluated by the measurement method described above. The results are shown in Table 1.

Examples 2-10
Pellets were obtained in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 1. However, in Example 4, pellets were obtained in the same manner as in Example 1 except that after blending the polyamide resin and the flame retardant, silicone oil was blended and supplied from the base. The obtained pellets were molded in the same manner as in the examples, and various properties were evaluated. The results are shown in Table 1.
Comparative Examples 1-6
Pellets were obtained in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 1. The obtained pellets were molded in the same manner as in the examples, and various properties were evaluated. The results are shown in Table 2.

  Since Examples 1 to 10 satisfy the requirements of the present invention, resin compositions having excellent mechanical properties and flame retardancy were obtained.

  However, Comparative Examples 1 and 2 are poor in operability because they are used in combination with flame retardants other than those based on the present invention. In Comparative Example 3, since there are few inorganic fillers, the flexural modulus is low, and Comparative Example 4 contains silicone oil. Therefore, Comparative Example 5 is inferior in releasability, and since Comparative Example 5 has many inorganic fillers, melt kneading cannot be performed, pellets cannot be obtained, and various physical properties cannot be measured, and Comparative Example 6 has a large amount of silicone oil. In addition, mold deposits increase, hindering molding, and problems in practical use.

Claims (4)

(A) Polyamide resin 20-60% by mass, (B) Inorganic filler 40-70% by mass, (C) 5-20% by mass of a flame retardant containing no halogen element, and the flame retardant is represented by formula (I) A phosphinate represented by formula (II) and / or a diphosphinate represented by formula (II), wherein 0.2 ≦ (C) / (A) ≦ 0.4, wherein (A), (B) When the resin composition obtained by blending (C) is 100 parts by mass, (D) 0.05 to 2 parts by mass of silicone oil is included, and 0.001 ≦ (D) / (A) ≦ 0.1 Flame retardant glass fiber reinforced polyamide resin composition.
(Wherein R ₁ , R ₄ and R ₂ , R ₅ are each linear or branched C ₁ -C ₁₆ alkyl, preferably C ₁ -C ₈ alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-octyl, and phenyl, and R ₁ and R ₂ and R ₄ and R ₅ may form a ring with each other, and R ₃ is linear or branched. C ₁ -C ₁₀ alkylene, in particular methylene, ethylene, n- propylene, isopropylene, isopropylidene, n- butylene, tert- butylene, n- pentylene, n- octylene, n- dodecylene; arylene, in particular phenylene, naphthylene, alkyl Arylene, especially methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene; arylalkylene, especially phenylmethylene, phenylethylene , Phenylpropylene, phenylbutylene, M is calcium or aluminum ion, m is 2 or 3, n is 1 or 3, and x is 1 or 2. mx = 2n in formula (II) .) The flame retardant glass fiber reinforced polyamide resin composition according to claim 1, wherein the inorganic filler is a flat glass fiber having a flat cross section having a major axis / minor axis ratio of 1.5 to 10. The silicone oil is a methylphenyl silicone oil having a specific gravity (25 ° C) of 1.03 to 1.06 and a kinematic viscosity (25 ° C) of 100 to 300 mm ² / s. The flame-retardant glass fiber reinforced polyamide resin composition described in 1. The molded product having a thickness of 1/32 inch obtained by molding a flame retardant glass fiber reinforced polyamide resin composition is V-0 by a flammability test according to safety standard UL94. The flame-retardant glass fiber reinforced polyamide resin composition according to any one of the above.