JPWO2019107096A1 - Polyamide resin composition and molded article obtained by molding the polyamide resin composition - Google Patents

Abstract

A resin composition containing 20 to 95% by mass of polyamide (A), 5 to 50% by mass of fibrous reinforcing material (B), and 1.5 to 20% by mass of plate-like filler (C). A) contains a polyamide (A1) having a melting point of 270 ° C. or higher and a polyamide (A2) having a melting point of less than 270 ° C., and the mass ratio of the polyamide (A1) to the polyamide (A2) (A1 / A2). The thermoplastic resin composition is 90/10 to 40/60, and the average particle size of the plate-shaped filler (C) is 4.5 to 60 μm.

Description

The present invention relates to a polyamide resin composition and a molded product obtained by molding the polyamide resin composition.

Polyamide has excellent heat resistance and mechanical properties, and is used as a constituent material for many electric / electronic parts and automobile parts.

Of these components, surface mounting is the mainstream for electrical and electronic components, and in the reflow soldering process, the polyamide molded body that constitutes the component is exposed to a high temperature of about 260 ° C. at the maximum temperature. Therefore, there are many cases where it is necessary to use a heat-resistant polyamide having a melting point of 270 ° C. or higher, which has reflow resistance, as the polyamide. In a molded product made of a resin having insufficient reflow resistance, problems such as discoloration, deformation, and blisters (blisters) occur after the reflow soldering process. Further, electrical and electronic parts tend to be miniaturized year by year, and the polyamide molded body constituting the parts is required to have thinner wall performance. In particular, flame retardancy and fluidity generally deteriorate as the molded product has a thinner wall thickness, and improvements thereof are strongly desired. Furthermore, electrical and electronic components also require mechanical strength that can withstand stress during assembly and terminal attachment / detachment.

As described above, in designing a heat-resistant polyamide suitable for electric / electronic parts, it is very important to achieve both reflow resistance, flame retardancy, fluidity, and strength.

With respect to these problems, Patent Documents 1 and 2 disclose a polyamide resin composition containing a specific semi-aromatic polyamide and a specific aliphatic polyamide. This composition has improved fluidity as compared with a composition containing only a semi-aromatic polyamide as a polyamide component, but has high reflow resistance, especially water absorption, which is a weak point of polyamide. From a point of view, it is still inadequate.

On the other hand, in Patent Document 3, a resin composition containing polyphenylene sulfide and crystalline polyamide contains at least one fine particle selected from the talc, silica, and kaolin groups having an average particle size of 4 μm or less. It is disclosed that the occurrence of blister can be suppressed. Further, Patent Document 4 discloses that blister can be suppressed by containing 0.01 to 1% by mass of a crystal nucleating agent in a flame-retardant resin composition containing nylon 46 and an aromatic polyamide. .. However, the resin composition of Patent Document 3 contains polyphenylene sulfide having low water absorption as a main component, and the same effect cannot always be obtained in a resin composition containing polyamide as a main component. Further, the resin composition of Patent Document 4 has insufficient fluidity because both of the constituent polyamides have a melting point of 270 ° C. or higher. Moreover, the resin composition is merely an improved blister in a molded product having a wall thickness of 0.5 mm. Even if the electrical and electronic parts are thin and miniaturized, there are many cases where a thick part of about 2 mm exists, and blisters are likely to occur in this thick part. Therefore, improvement of the blister in the thick part is desired. There is.

Japanese Patent Publication No. 2014-517102 Special Table 2014-521765 Japanese Unexamined Patent Publication No. 10-130502 Japanese Unexamined Patent Publication No. 6-65502

The present invention solves the above-mentioned problems in the polyamide resin composition, and provides a polyamide resin composition capable of simultaneously satisfying fluidity and mechanical strength while suppressing the generation of blister during the reflow process. The purpose.

As a result of intensive studies to solve the above problems, the present inventors have contained a specific polyamide (A1) and a specific polyamide (A2) in a specific mass ratio as the polyamide constituting the polyamide resin composition. We have found that the above-mentioned problems can be solved by blending a fibrous reinforcing material and a plate-shaped filler having a specific shape, and have reached the present invention. That is, the gist of the present invention is as follows.

(1) A resin composition containing 20 to 95% by mass of polyamide (A), 5 to 50% by mass of fibrous reinforcing material (B), and 1.5 to 20% by mass of plate-like filler (C). ,
The polyamide (A) contains a polyamide (A1) having a melting point of 270 ° C. or higher and a polyamide (A2) having a melting point of less than 270 ° C.
The mass ratio (A1 / A2) of the polyamide (A1) to the polyamide (A2) is 90/10 to 40/60.
A polyamide resin composition characterized in that the average particle size of the plate-shaped filler (C) is 4.5 to 60 μm.
(2) The polyamide resin composition according to (1), wherein the polyamide (A1) is a semi-aromatic polyamide.
(3) The polyamide resin composition according to (1) or (2), wherein the plate-shaped filler (C) is talc.
(4) The polyamide resin composition according to any one of (1) to (3), wherein the plate-shaped filler (C) is surface-treated.
(5) The polyamide resin composition according to any one of (1) to (4), further containing the flame retardant (D) in an amount of 30% by mass or less.
(6) The polyamide resin composition according to (5), wherein the flame retardant (D) is a non-halogen flame retardant.
(7) The polyamide resin composition according to (5), wherein the flame retardant (D) is a halogen-based flame retardant.
(8) A molded product obtained by molding the polyamide resin composition according to any one of (1) to (7) above.
(9) A surface mount component comprising the molded product according to (8) above.

According to the present invention, by blending a fibrous reinforcing material and a specific plate-like filler in a polyamide resin composition containing a specific polyamide (A1) and a specific polyamide (A2) in a specific mass ratio. , A polyamide resin composition capable of simultaneously satisfying reflow resistance, high fluidity, and high strength, and a resin composition having both high flame retardancy can be provided by further blending a flame retardant. It is very surprising that blister can be suppressed during the reflow process despite the fact that it contains a large amount of polyamide (A2) having a low melting point.

Hereinafter, the present invention will be described in detail.
The polyamide resin composition of the present invention contains a polyamide (A1), a polyamide (A2), a fibrous reinforcing material (B), and a plate-like filler (C).

The polyamide (A1) in the present invention contains a dicarboxylic acid component and a diamine component. Examples of the dicarboxylic acid component include terephthalic acid (TPA), isophthalic acid and its derivatives, naphthalenedicarboxylic acid and its derivatives, adipic acid, sebacic acid, azelaic acid, dodecanedic acid and the like, and among them, terephthalic acid is preferable. ..

Examples of the diamine component constituting the polyamide (A1) include C6-C20 aromatic diamine, C6-C20 alicyclic diamine, butanediamine, hexamethylenediamine, 2-methylpentamethylenediamine, and 2-methyloctamethylenediamine. Aliphatic diamines such as trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane can be mentioned.

The polyamide (A1) in the present invention needs to have a melting point of 270 ° C. or higher, preferably 280 ° C. or higher, and more preferably 300 ° C. or higher. Since the polyamide (A1) has a melting point of 270 ° C. or higher, it has heat resistance and can withstand a reflow step in which the maximum temperature is about 260 ° C. On the other hand, when the melting point of the polyamide (A1) exceeds 350 ° C., the decomposition temperature of the amide bond is about 350 ° C., so that carbonization and decomposition may proceed during the melt processing. In addition, since it is necessary to raise the temperature during molding to a melting point or higher, metal corrosion will progress more.
From the viewpoint of the melting point, the polyamide (A1) is preferably polyamide 46, polyamide 4T, polyamide 6T, polyamide 8T, polyamide 9T, polyamide 10T, polyamide 11T, polyamide 12T and a copolymer thereof. Further, semi-aromatic polyamides such as polyamide 4T, polyamide 6T, polyamide 9T, polyamide 10T, and copolymers thereof are more preferable because they have an excellent balance between water absorption and heat resistance and are particularly excellent in reflow resistance. Of these, polyamide 10T and its copolymer are particularly preferable. As the polyamide (A1), these polyamides may be used alone, or a mixture of two or more kinds of polyamides may be used.

In the present invention, the polyamide (A1) can contain a monocarboxylic acid component as a constituent component. The content of the monocarboxylic acid component is preferably 0.3 to 4.0 mol%, preferably 0.3 to 3.0 mol%, based on all the monomer components constituting the polyamide (A). More preferably, it is more preferably 0.3 to 2.5 mol%, and particularly preferably 0.8 to 2.5 mol%. By containing the monocarboxylic acid component within the above range, the polyamide (A1) can reduce the molecular weight distribution during polymerization, and the obtained resin composition can be seen to have improved releasability during molding. , The amount of gas generated during molding can be suppressed. On the other hand, if the content of the monocarboxylic acid component exceeds the above range, the obtained molded product may have reduced mechanical properties and flame retardancy. In the present invention, the content of the monocarboxylic acid refers to the ratio of the residue of the monocarboxylic acid in the polyamide (A), that is, the monocarboxylic acid desorbed from the terminal hydroxyl group.

The polyamide (A) preferably contains a monocarboxylic acid having a molecular weight of 140 or more as a monocarboxylic acid component, and more preferably contains a monocarboxylic acid having a molecular weight of 170 or more. When the molecular weight of the monocarboxylic acid is 140 or more, the obtained resin composition has improved releasability, can suppress the amount of gas generated at the temperature during molding, and also has improved molding fluidity. be able to.

Examples of the monocarboxylic acid component include aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, and aromatic monocarboxylic acid. Among them, the amount of gas generated by the polyamide-derived component is reduced, mold stains are reduced, and separation is performed. Aliphatic monocarboxylic acids are preferred because they can improve moldability.

Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Of these, stearic acid is preferable because of its high versatility.
Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid.
Examples of aromatic monocarboxylic acids having a molecular weight of 140 or more include 4-ethylbenzoic acid, 4-hexylbenzoic acid, 4-laurylbenzoic acid, 1-naphthoic acid, 2-naphthoic acid and derivatives thereof. ..

The monocarboxylic acid component may be used alone or in combination. Further, a monocarboxylic acid having a molecular weight of 140 or more and a monocarboxylic acid having a molecular weight of less than 140 may be used in combination. In the present invention, the molecular weight of the monocarboxylic acid refers to the molecular weight of the raw material monocarboxylic acid.

The polyamide (A1) can be produced by using a conventionally known method of heat polymerization method or solution polymerization method. Among them, the heat polymerization method is preferably used because it is industrially advantageous.

The polyamide (A2) in the present invention needs to have a melting point of less than 270 ° C.
Examples of the polyamide (A2) include polyamide 6, polyamide 66, polyamide 10, polyamide 610, polyamide 612, polyamide 1010, polyamide 11, polyamide 12, a copolymer of metaxylylene diamine and adipic acid (polyamide MXD6), and polyamide 66. / 6 copolymer, copolymer of paraaminomethylbenzoic acid and ε-caprolactam (polyamide AHBA), 2,2,4- / 2,4,4-trimethylhexamethylenediamine / terephthalate as main components Polyamide (polyamide THDT, THDT / 6I) and the like can be mentioned. Among them, from the viewpoint of fluidity, polyamide 6, polyamide 66, polyamide 10, polyamide 610, polyamide 612, polyamide 1010, polyamide 11, and polyamide 12 are preferable, and polyamide 6 and polyamide 66 are more preferable.

In the polyamide resin composition of the present invention, the content of the polyamide (A) needs to be 20 to 95% by mass, and preferably 35 to 50% by mass. When the content of the polyamide (A) is less than 20% by mass, the resin composition has extremely low fluidity or low strength due to insufficient toughness. On the other hand, when the content of the polyamide (A) is 95% by mass or more, the resin composition is inferior in terms of reflow resistance and strength because there are few other components.

Further, the mass ratio (A1 / A2) of the polyamide (A1) and the polyamide (A2) constituting the polyamide (A) needs to be 90/10 to 40/60, and is 70/30 to 45/55. Is preferable. If the mass ratio (A1 / A2) is out of this range, the resin composition becomes unusable for practical use due to a decrease in fluidity and a decrease in reflow resistance.

The polyamide resin composition of the present invention contains a fibrous reinforcing material (B). The fibrous reinforcing material (B) is not particularly limited, and for example, glass fiber, carbon fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, total aromatic polyamide fiber, polybenzoxazole fiber, Polytetrafluoroethylene fiber, Kenaf fiber, bamboo fiber, hemp fiber, bagas fiber, high-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless fiber, steel fiber, ceramics fiber, genbuiwa fiber Can be mentioned. Among them, glass fiber, carbon fiber, and metal fiber are preferable because they have a high effect of improving mechanical properties, have heat resistance that can withstand the heating temperature at the time of melt-kneading with polyamide (A), and are easily available. The fibrous reinforcing material may be used alone or in combination.

The glass fiber and carbon fiber are preferably surface-treated with a silane coupling agent. The silane coupling agent may be dispersed in the sizing agent. Examples of the silane coupling agent include vinylsilane-based, acrylicsilane-based, epoxysilane-based, and aminosilane-based, and among them, the aminosilane-based cup has a high adhesion effect between the polyamide (A) and the glass fiber or carbon fiber. Ring agents are preferred.

The fiber length and fiber diameter of the fibrous reinforcing material are not particularly limited, but the fiber length is preferably 0.1 to 7 mm, more preferably 0.5 to 6 mm. Since the fiber length of the fibrous reinforcing material is 0.1 to 7 mm, the resin composition can be reinforced without adversely affecting the moldability. The fiber diameter is preferably 3 to 20 μm, more preferably 5 to 13 μm. Since the fiber diameter is 3 to 20 μm, the resin composition can be reinforced without breaking during melt kneading.
Examples of the cross-sectional shape of the fibrous reinforcing material include a circular shape, a rectangular shape, an elliptical shape, and other irregular cross-sectional shapes, and a circular shape is preferable.

The content of the fibrous reinforcing material (B) in the resin composition of the present invention needs to be 5 to 50% by mass, preferably 25 to 45% by mass. When the content of the fibrous reinforcing material (B) is less than 5% by mass, the resin composition has a small effect of improving mechanical properties and is inferior in reflow resistance. On the other hand, when the content of the fibrous reinforcing material (B) exceeds 50% by mass, the effect of improving the mechanical properties of the resin composition is saturated, and not only the effect of improving the mechanical properties cannot be expected, but also the fluidity becomes poor. Since it is extremely lowered, it becomes difficult to obtain a molded product.

The polyamide resin composition of the present invention further contains a plate-like filler (C). The plate-shaped filler (C) is not particularly limited, and examples thereof include talc, mica, glass flakes, graphite, and metal foil. Of these, talc and mica are preferable, and talc is particularly preferable, as those having a high blister suppressing effect during the reflow process. The plate-shaped filler may be used alone or in combination of two or more.

The plate-shaped filler (C) may be surface-treated with an organic compound such as a silane coupling agent. By surface treatment, the adhesion to the polyamide (A) is improved, which is effective in improving the strength and suppressing blisters.

The average particle size of the plate-shaped filler (C) needs to be 4.5 to 60 μm, preferably 5 to 50 μm, and more preferably 10 to 30 μm. In the present invention, it is surprising to find that the generation of blister during the reflow process can be effectively suppressed by using the plate-shaped filler (C) having an average particle size within the above range. That is. If the average particle size deviates from the above range, the blister suppressing effect is greatly impaired. Further, when the average particle size exceeds 60 μm, the decrease in mechanical strength becomes large. The average particle size in the present invention refers to the median diameter (D50) obtained by the laser diffraction method.

The content of the plate-shaped filler (C) in the resin composition of the present invention needs to be 1.5 to 20% by mass, preferably 3 to 15% by mass, and 5 to 10% by mass. Is more preferable. When the content of the plate-shaped filler (C) is less than 1.5% by mass, the blister suppressing effect at the time of the reflow step is small. On the other hand, when the content of the plate-shaped filler (C) exceeds 20% by mass, the fluidity and mechanical strength of the resin composition are lowered.

The polyamide resin composition of the present invention contains a flame retardant (D), if necessary. Examples of the flame retardant (D) include halogen-based flame retardants and non-halogen flame retardants. Examples of non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, nitrogen-phosphorus flame retardants, and inorganic flame retardants. Among them, phosphorus flame retardants are selected from the viewpoint of heat resistance and flame retardancy. More preferred.

Examples of the phosphorus-based flame retardant include phosphinic acid metal salts. Examples of the phosphinic acid metal salt include a phosphinic acid metal salt represented by the following general formula (I) and a diphosphinic acid metal salt represented by the general formula (II).

In the formula, R ¹ , R ² , R ⁴ and R ⁵ each need to be an alkyl group or a phenyl group having 1 to 16 carbon atoms in a straight chain or a branched chain, respectively, and have 1 to 8 carbon atoms. Is preferably an alkyl group or a phenyl group, and is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-octyl group, or a phenyl group. More preferably, it is more preferably an ethyl group. R ¹ and R ² and R ⁴ and R ⁵ may form rings with each other.
R ³ needs to be a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group. Examples of the alkylene group having 1 to 10 carbon atoms in the linear or branched chain include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, an n-butylene group, a tert-butylene group and an n-. Examples thereof include a pentylene group, an n-octylene group and an n-dodecylene group. Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group. Examples of the alkylarylene group include a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group and a tert-butylnaphthylene group. Examples of the arylalkylene group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group.
M represents a metal ion. Examples of the metal ion include calcium ion, aluminum ion, magnesium ion and zinc ion, and aluminum ion and zinc ion are preferable, and aluminum ion is more preferable.
m and n represent the valences of metal ions. m is 2 or 3. a represents the number of metal ions, b represents the number of diphosphane ions, and n, a, and b are integers satisfying the relational expression of “2 × b = n × a”.

The phosphinic acid metal salt and the diphosphinic acid metal salt are produced in an aqueous solution using the corresponding phosphinic acid and diphosphinic acid, respectively, and a metal carbonate, a metal hydroxide or a metal oxide, and usually exist as a monomer. Depending on the reaction conditions, it may exist in the form of a polymer phosphinate having a degree of condensation of 1-3.

Specific examples of the phosphinate represented by the above general formula (I) include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphine, ethylmethylphosphine. Magnesium acid, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphine, methyl-n-propylphosphine Magnesium Acid, Aluminum Methyl-n-propylphosphinate, Zinc Methyl-n-propylphosphinate, Calcium Methylphenylphosphinate, Magnesium Methylphenylphosphinate, Aluminum Methylphenylphosphinate, Zinc Methylphenylphosphine Examples thereof include magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. Among them, aluminum diethylphosphinate and zinc diethylphosphinate are preferable, and aluminum diethylphosphinate is more preferable, because they are excellent in flame retardancy and an excellent balance of electrical characteristics.

Examples of the diphosphinic acid used for producing the diphosphinate include methanedi (methylphosphinic acid) and benzene-1,4-di (methylphosphinic acid).

Specific examples of the diphosphinate represented by the above general formula (II) include calcium methanedi (methylphosphinic acid), magnesium methanedi (methylphosphinic acid), aluminum methanedi (methylphosphinic acid), and methanedi (methylphosphinic acid). ) Zinc, benzene-1,4-di (methylphosphinic acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, benzene-1,4 -Di (methylphosphinic acid) zinc can be mentioned. Of these, methanedi (methylphosphinic acid) aluminum and methanedi (methylphosphinic acid) zinc are preferable because they have an excellent balance of flame retardancy and electrical characteristics.

Specific products of the phosphinic acid metal salt include, for example, "Exolit OP1230", "Exolit OP1240", "Exolit OP1312", "Exolit OP1314", and "Exolit OP1400" manufactured by Clariant AG.

Examples of the nitrogen-based flame retardant include a melamine-based compound, cyanuric acid, or a salt of isocyanuric acid and a melamine compound. Specific examples of melamine-based compounds include melamine, melamine derivatives, compounds having a structure similar to melamine, and condensates of melamine. Specifically, melamine, ammeline, ammeline, formoguanamine, guanyl melamine, and cyano. Examples thereof include compounds having a triazine skeleton such as melamine, benzoguanamine, acetoguanamine, succinoguanamine, melam, melem, methone, and melon, and sulfates and melamine resins thereof. The salt of cyanuric acid or isocyanuric acid and a melamine compound is an equimolar reaction product of cyanuric acid or isocyanuric acid and a melamine compound.

Examples of the nitrogen-phosphorus flame retardant include an adduct (melamine adduct) formed from melamine or a condensation product thereof and a phosphorus compound, and a phosphazene compound.
Examples of the phosphorus compound constituting the melamine adduct include phosphoric acid, orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid and the like. Specific examples of the melamine adduct include melamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, and melamine polyphosphate, and among them, melamine polyphosphate is preferable. The number of phosphorus is preferably 2 or more, and more preferably 10 or more.
Specific products of the phosphazene compound include, for example, "Rabbitl FP-100" and "Rabbitl FP-110" manufactured by Fushimi Pharmaceutical Co., Ltd., "SPS-100" and "SPB-100" manufactured by Otsuka Chemical Co., Ltd. ..

Examples of the inorganic flame retardant include metal hydroxides such as magnesium hydroxide and calcium hydroxide, phosphates such as zinc borate and aluminum phosphate, phosphates such as aluminum phosphite, and calcium hypophosphite. Hypophosphates such as, calcium aluminate and the like. These inorganic flame retardants may be blended for either purpose of improving flame retardancy or reducing metal corrosiveness.

Examples of the halogen-based flame retardant include hexabromocyclododecane, bis (dibromopropyl) tetrabromo-bisphenol A, bis (dibromopropyl) tetrabromo-bisphenol S, tris (dibromopropyl) isocyanurate, and tris (tribromoneopentyl) phosphate. , Decabromodiphenylene oxide, brominated epoxy resin, bis (pentabromophenyl) ethane, tris (tribromophenoxy) triazine, ethylenebis (tetrabromophthal) imide, ethylenebispentabromophenyl, polybromophenylindane, brominated Examples thereof include polystyrene, tetrabromobisphenol A polycarbonate, brominated polyphenylene oxide, and polypentabromobenzyl acrylate. Of these, ethylenebis (tetrabromophthal) imide, brominated epoxy resin, and brominated polystyrene that can withstand processing at high temperatures are preferable, and brominated polystyrene is more preferable. These may be used alone or in combination.

The resin composition of the present invention does not have to contain the flame retardant (D), but when it contains the flame retardant, the upper limit of the content needs to be 30% by mass. The content of the flame retardant (D) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass in order to realize sufficient flame retardancy. If the content of the flame retardant (D) is less than 5% by mass, it becomes difficult to impart the required flame retardancy to the resin composition. On the other hand, when the content of the flame retardant (D) exceeds 30% by mass, the resin composition is excellent in flame retardancy, but melt kneading may be difficult, and the obtained molded product has mechanical properties. May be inadequate.

If necessary, other additives such as stabilizers, colorants, antistatic agents, flame retardant aids, and carbonization inhibitors may be further added to the polyamide resin composition of the present invention. Examples of the colorant include pigments such as titanium oxide, zinc oxide and carbon black, and dyes such as niglosin. Examples of the stabilizer include a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a light stabilizer, a heat stabilizer made of a copper compound, and a heat stabilizer made of alcohols. Examples of the flame retardant aid include metal salts such as zinc tinate, zinc borate, antimony trioxide, antimony pentoxide and sodium antimonate. The carbonization inhibitor is an additive that improves tracking resistance, and examples thereof include inorganic substances such as metal hydroxides and metal borate salts, and the above-mentioned heat stabilizers.

The method for producing the resin composition of the present invention is not particularly limited, but is added with polyamide (A1), polyamide (A2), fibrous reinforcing material (B), plate-like filler (C), and if necessary. A method in which a flame retardant (D) and other additives are blended and melt-kneaded is preferable. Examples of the melt-kneading method include a method using a batch kneader such as lavender, a Banbury mixer, a Henschel mixer, a helical rotor, a roll, a single-screw extruder, a twin-screw extruder and the like. The melt-kneading temperature is selected from the region where the polyamide (A1) and the polyamide (A2) are melted and do not decompose. If the melt-kneading temperature is too high, not only the polyamide (A1) and polyamide (A2) may be decomposed, but also the flame retardant (D) may be decomposed. Therefore, assuming that the melting point of the polyamide (A1) is Tm. It is preferably (Tm-20 ° C.) to (Tm + 50 ° C.).

As a method for processing the polyamide resin composition of the present invention into various shapes, a method of extruding the molten mixture into a strand shape into a pellet shape, a method of hot-cutting and underwater-cutting the molten mixture into a pellet shape, and a method Examples thereof include a method of extruding into a sheet and cutting, and a method of extruding into a block and pulverizing to form a powder.

The molded product of the present invention is formed by molding the above-mentioned polyamide resin composition.
Examples of the molding method include an injection molding method, an extrusion molding method, a blow molding method, a sintering molding method, and a compression molding method. The injection molding method is preferable because it has a great effect of improving mechanical properties and moldability. ..
The injection molding machine is not particularly limited, and examples thereof include a screw in-line type injection molding machine and a plunger type injection molding machine. The polyamide resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled and solidified in a predetermined shape, and then molded from the mold. Taken out. The resin temperature at the time of injection molding is preferably heat-melted at a melting point (Tm) or higher of the polyamide (A1) and more preferably less than (Tm + 50 ° C.).
When the polyamide resin composition is heated and melted, it is preferable to use sufficiently dried polyamide resin composition pellets. If the amount of water contained is large, the resin may foam in the cylinder of the injection molding machine, making it difficult to obtain an optimum molded product. The water content of the polyamide resin composition pellets used for injection molding is preferably less than 0.3 parts by mass and more preferably less than 0.1 parts by mass with respect to 100 parts by mass of the polyamide resin composition.

The polyamide resin composition of the present invention is excellent in reflow resistance, mechanical strength, and fluidity, and the polyamide resin composition containing the flame retardant (D) is also excellent in flame retardancy. It can be used for automobile parts, electrical / electronic parts, miscellaneous goods, industrial equipment parts, civil engineering and construction supplies, etc. Of these, it can be used for surface mount component applications that require a reflow process in particular.
Examples of automobile parts include thermostat members, inverter IGBT module members, insulators, motor insulators, exhaust finishers, power device housings, ECU housings, motor members, coil members, cable covering materials, in-vehicle camera housings, and the like. Automotive camera lens holder, automotive connector, engine mount, intercooler, bearing retainer, oil seal ring, chain cover, ball joint, chain tensioner, starter gear, reducer gear, automotive lithium ion battery tray, automotive high voltage fuse Cases and turbocharger impellers for automobiles can be mentioned.
Electrical and electronic components include, for example, connectors, ECU connectors, Mayten lock connectors, modular jacks, reflectors, LED reflectors, switches, sensors, sockets, pin sockets, capacitors, jacks, fuse holders, relays, coil bobbins, breakers, circuits. Parts, electromagnetic switches, holders, covers, plugs, housing parts for electrical and electronic devices such as portable personal computers, impellers, vacuum cleaner impellers, resistors, variable resistors, ICs, LED housings, camera housings, Camera barrel, camera lens holder, tact switch, tact switch for lighting, hair iron housing, hair iron comb, small switch for all mold DC, organic EL display switch, material for 3D printer, material for bond magnet for motor Can be mentioned.
Examples of miscellaneous goods include trays, sheets, and cable ties.
Examples of industrial equipment parts include insulators, connectors, gears, switches, sensors, impellers, and Plarail chains.
Examples of civil engineering and construction supplies include fences, storage boxes, construction switchboards, anchor bolt guides, anchor rivets, and solar panel raising materials.
Among them, the polyamide resin composition of the present invention containing the flame retardant (D) is particularly excellent in flame retardancy, and therefore can be suitably used for electrical and electronic parts.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

1. 1. Measurement method The physical properties of the polyamide and polyamide resin composition were measured by the following methods.

(1) Melting point Using a differential scanning calorimeter (DSC-7 type manufactured by PerkinElmer), the temperature is raised to 350 ° C at a heating rate of 20 ° C / min, held at 350 ° C for 5 minutes, and the temperature is lowered at a rate of 20 ° C / min. The temperature was lowered to 25 ° C., and the temperature was further maintained at 25 ° C. for 5 minutes, and then the top of the heat absorption peak when the temperature was raised again at a heating rate of 20 ° C./min was defined as the melting point (Tm).

(2) Using an injection molding machine ROBOSHOT S2000i (manufactured by FANUC), the fluidity polyamide resin composition was set to a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C., a mold clamping force of 100 tons, and an injection pressure of 80 MPa. Under the conditions of an injection speed of 120 mm / sec and an injection time of 5 seconds, a special mold for a one-point gate on one side was attached to the tip of the cylinder for molding, and the bar flow flow length was measured. The dedicated mold has a shape that allows an L-shaped molded body having a thickness of 0.2 mm and a width of 20 mm to be collected, has a gate at the center of the upper part of the L-shape, and has a maximum flow length of 150 mm. Practically, the flow length is preferably 10 mm or more.

(3) Reflow resistance Polyamide resin composition is injection molded using an injection molding machine J35AD (manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C., and has a size of 20 mm × 20 mm × 2 mm. A test piece was prepared. The obtained test molded piece was subjected to a moisture absorption treatment at 85 ° C. × 85% RH for 168 hours, and then heated at 150 ° C. for 1 minute in an infrared heating type reflow furnace at a rate of 100 ° C./min. The temperature was raised to 265 ° C. and held for 10 seconds.
In the test piece after heat treatment, "5" is when the area ratio of blisters (blisters) generated on the surface of the test piece is 0%, and "5" is when it is larger than 0% and 25% or less. 4 ”, the case of greater than 25% and 50% or less was evaluated as“ 3 ”, the case of greater than 50% and 75% or less was evaluated as“ 2 ”, and the case of greater than 75% was evaluated as“ 1 ”.

(4) Tensile Strength An ISO-compliant test piece was prepared from the polyamide resin composition using an injection molding machine ROBOSHOT S2000i (manufactured by FANUC) under the conditions of a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C. The tensile strength of the obtained test piece was measured according to ISO527. Practically, the tensile strength is preferably 80 MPa or more.

(5) The flame-retardant polyamide resin composition is injection-molded using an injection molding machine J35AD (manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 330 ° C. and a mold temperature of 170 ° C., 127 mm × 12.7 mm × A 0.3 mm test piece was prepared. Using the obtained test pieces, flame retardancy was evaluated according to the UL94 (standard defined by Under Writer's Laboratories Inc. in the United States) shown in Table 1. The shorter the total residual flame time, the better the flame retardancy. From the viewpoint of flame retardancy, the residual flame time is preferably 50 seconds or less.

2. 2. Raw Materials The raw materials used in Examples and Comparative Examples are shown below.

(1) Polyamide / Polyamide (A1-1)
4.70 kg of powdered terephthalic acid (TPA) as a dicarboxylic acid component, 0.32 kg of stearic acid (STA) as a monocarboxylic acid component, and 9.3 g of sodium hypophosphate monohydrate as a polymerization catalyst. The mixture was placed in a ribbon blender type reactor, sealed with nitrogen, and heated to 170 ° C. with stirring at a rotation speed of 30 rpm. Then, while keeping the temperature at 170 ° C. and the rotation speed at 30 rpm, 4.98 kg of 1,10-decanediamine (DDA) heated to 100 ° C. as a diamine component using a liquid injection device was added to 2 . Addition was carried out continuously (continuous liquid injection method) over 5 hours to obtain a reaction product. The molar ratio of the raw material monomer is TPA: DDA: STA = 48.5: 49.6: 1.9 (the equivalent ratio of the functional groups of the raw material monomer is TPA: DDA: STA = 49.0: 50.0). : 1.0).
Subsequently, the obtained reaction product was polymerized by heating it in the same reactor under a nitrogen stream at 250 ° C. and a rotation speed of 30 rpm for 8 hours to prepare a polyamide powder.
Then, the obtained polyamide powder was formed into strands using a twin-screw kneader, the strands were passed through a water tank to be cooled and solidified, and the strands were cut with a pelletizer to obtain polyamide (A-1) pellets.

-Polyamide (A1-2) to (A1-4), polyamide (A2-2)
Polyamides (A1-2) to (A1-4) and polyamides (A2-2) were obtained in the same manner as the polyamides (A1-1) except that the resin composition was changed as shown in Table 2.

Table 2 shows the resin composition and characteristic values of the above-mentioned polyamide.

-Polyamide (A1-5)
As the polyamide (A1-5), polyamide 46 (TW300 melting point 290 ° C. manufactured by DSM) was used.
-Polyamide (A2-1)
As the polyamide (A2-1), polyamide 66 (Leona 1200 manufactured by Asahi Kasei Chemicals Co., Ltd., melting point 265 ° C.) was used.

(2) Fibrous reinforcing material (B)
・ B-1 glass fiber (03JAFT692 manufactured by Asahi Fiber Glass, average fiber diameter 10 μm, average fiber length 3 mm)
-B-2 carbon fiber (TR06NEB4 manufactured by Mitsubishi Rayon, average fiber diameter 6 μm, average fiber length 6 mm)

(3) Plate-shaped filler (C)
・ C-1 talc (MS-P average particle size 15 μm manufactured by Nippon Talc)
・ C-2 talc (GH-7, manufactured by Hayashi Kasei Co., Ltd., average particle size 6 μm)
・ C-3 mica (A-41S manufactured by Yamaguchi Mica, average particle size 47 μm)
・ C-4 talc (MSZ-C average particle size 11 μm surface treated product manufactured by Nippon Talc)
・ C-5 talc (SG-2000 average particle size 1 μm manufactured by Nippon Talc)
・ C-6 mica (Suzorite150-NY manufactured by Imerys, average particle size 90 μm)

(4) Flame retardant (D)
-D-1: Aluminum diethylphosphine (Exolit OP1230 manufactured by Clariant)
D-2: Mixture of brominated polystyrene (Great Lakes PDBS-80 manufactured by LANXESS) and zinc nitrate (Flamtard S manufactured by William Blythe) in a mass ratio of 5/1.

Example 1
27 parts by mass of polyamide (A1-1), 33 parts by mass of polyamide (A2-1), and 10 parts by mass of plate-like filler (C-1) are dry-blended, and a loss-in weight type continuous quantitative supply device (CE manufactured by Kubota Co., Ltd.) -W-1 type) was used for weighing, and the mixture was supplied to the main supply port of a uniaxial twin-screw extruder (TEM26SS type manufactured by Toshiba Machine Co., Ltd.) having a screw diameter of 26 mm and L / D50, and melt-kneaded. On the way, 30 parts by mass of the fibrous reinforcing material (B-1) was supplied from the side feeder, and further kneading was performed. After being taken into a strand shape from the die, it was passed through a water tank to be cooled and solidified, and this was cut with a pelletizer to obtain a polyamide resin composition pellet. The barrel temperature of the extruder was set (melting point −5 to + 15 ° C.), screw rotation speed 250 rpm, and discharge rate 25 kg / h.

Examples 2-18, Comparative Examples 1-9
The same operation as in Example 1 was carried out except that the composition of the polyamide resin composition was changed as shown in Tables 3 and 5, to obtain polyamide resin composition pellets.

Example 19
21.8 parts by mass of polyamide (A1-1), 26.7 parts by mass of polyamide (A2-1), 1.5 parts by mass of plate-like filler (C-1), 20 parts by mass of flame retardant (D-1) The same operation as in Example 1 was carried out except for the dry blending to obtain polyamide resin composition pellets.

Examples 20-37, Comparative Examples 10-18
The same operation as in Example 19 was carried out except that the composition of the polyamide resin composition was changed as shown in Tables 4 to 5, to obtain polyamide resin composition pellets.

Various evaluation tests were carried out using the obtained polyamide resin composition pellets. The results are shown in Tables 3-5.

Since the resin compositions of Examples 1 to 37 satisfy the requirements of the present invention, the resin compositions of Examples 19 to 37 are excellent in fluidity and tensile strength while reducing the generation of blister during the reflow step. It was excellent in flame retardancy.

The resin compositions of Comparative Examples 1 and 10 had insufficient reflow resistance because the content of the plate-shaped filler (C) was too small. Further, the resin compositions of Comparative Examples 2 and 11 had an excessive content of the plate-like filler (C), and therefore had excellent reflow resistance but were inferior in fluidity and tensile strength.
Since the resin compositions of Comparative Examples 3 and 12 did not contain the fibrous reinforcing material (B), they were inferior in reflow resistance and tensile strength, and the resin composition of Comparative Example 12 contained a flame retardant (D). Was also inferior in flame retardancy.
The resin compositions of Comparative Examples 4 and 13 contained an excessive amount of the fibrous reinforcing material (B), and the resin compositions of Comparative Examples 5 and 14 had a melting point of less than 270 ° C. (A2). In both cases, the fluidity was very low, and in the fluidity test, the resin solidified before passing through the gate of the bar flow mold, making it impossible to measure the flow length.
The resin compositions of Comparative Examples 6 and 15 contained too low a polyamide (A1) having a melting point of 270 ° C. or higher, and the resin compositions of Comparative Examples 7 and 16 did not contain any polyamide (A1). , It was inferior in reflow resistance.
The resin compositions of Comparative Examples 8 and 17 were inferior in reflow resistance because the average particle size of the plate-shaped filler (C) was too small, and the resin compositions of Comparative Examples 9 and 18 were Since the average particle size of the plate-shaped filler (C) was excessive, the tensile strength was inferior.

Claims (9)

A resin composition containing 20 to 95% by mass of polyamide (A), 5 to 50% by mass of fibrous reinforcing material (B), and 1.5 to 20% by mass of plate-like filler (C).
The polyamide (A) contains a polyamide (A1) having a melting point of 270 ° C. or higher and a polyamide (A2) having a melting point of less than 270 ° C.
The mass ratio (A1 / A2) of the polyamide (A1) to the polyamide (A2) is 90/10 to 40/60.
A polyamide resin composition characterized in that the average particle size of the plate-shaped filler (C) is 4.5 to 60 μm. The polyamide resin composition according to claim 1, wherein the polyamide (A1) is a semi-aromatic polyamide. The polyamide resin composition according to claim 1 or 2, wherein the plate-shaped filler (C) is talc. The polyamide resin composition according to any one of claims 1 to 3, wherein the plate-shaped filler (C) is surface-treated. The polyamide resin composition according to any one of claims 1 to 4, further containing 30% by mass or less of the flame retardant (D). The polyamide resin composition according to claim 5, wherein the flame retardant (D) is a non-halogen flame retardant. The polyamide resin composition according to claim 5, wherein the flame retardant (D) is a halogen-based flame retardant. A molded product obtained by molding the polyamide resin composition according to any one of claims 1 to 7. A surface mount component comprising the molded product according to claim 8.