JP5800096B2 - Flame retardant polyamide resin composition - Google Patents

Description

  The present invention provides a molded article obtained by using a polyamide resin composition having a high melting point and flame-retarded with a non-halogen flame retardant, so that bleed-out does not occur in the use environment, and even in a high-temperature and high-humidity environment. The present invention relates to a flame retardant polyamide resin composition capable of exhibiting stable mechanical properties and dimensional stability.

  Among thermoplastic resins, polyamide resins have been used for clothing, industrial material fibers, engineering plastics and the like, taking advantage of their excellent properties and ease of melt molding. In particular, engineering plastics are used not only for automobile parts and industrial machine parts but also for various industrial parts, housing parts, electrical and electronic parts, and so on.

  With regard to electrical and electronic components, in recent years, surface mounting methods (flow method, reflow method) have been adopted in the mounting due to the miniaturization of components accompanying the miniaturization of product size, higher mounting density, simplification of processes, and lower costs. It is rapidly penetrating. In the surface mounting method, since the process atmosphere temperature is equal to or higher than the solder melting temperature (240 to 260 ° C.), the resin to be used is inevitably required to have heat resistance at the above atmospheric temperature. Further, in the surface mounting process, the swelling and deformation of the mounting component due to the water absorption of the resin may be a problem, and the resin used is required to have low water absorption. As resins that satisfy these characteristics, aromatic polyamides such as 6T polyamides are used in surface mount electric and electronic parts.

  On the other hand, it is desirable that the polyamide resin as a raw material has flame retardancy based on the UL-94 standard depending on the location and environment of the molded product formed of the polyamide resin. In response to such a need, various technical developments for imparting flame retardancy to polyamide resins have been performed so far. As a technique for flame-retarding a polyamide resin, a combined use of a halogenated organic compound such as brominated polystyrene as a flame retardant and an antimony compound that works as a flame retardant aid is common. However, while this technology can provide excellent flame retardancy, it has problems such as generation of hydrogen halide during combustion and a large amount of smoke generation. Furthermore, since the use of plastic products using some halogenated flame retardants is being regulated, non-halogen flame retardant polyamide resins are being actively studied.

  As non-halogen flame retardant technologies, those using metal hydroxides or phosphorus compounds as flame retardants are common, but the former requires a large amount of addition to obtain sufficient flame retardancy, As a result, there is a problem that the mechanical properties are remarkably deteriorated.

  On the other hand, in the latter, for example, in Patent Document 1, a high flame retardant property is imparted to the polyamide 66 by using a phosphorus compound containing melamine, melam, and melem as structural units in the triazine compound as a flame retardant. Non-halogen flame retardant polyamide resin compositions have been proposed. Patent Document 2 proposes a non-halogen flame retardant polyamide resin composition in which flame resistance is imparted to the polyamide 46 by the combined use of a nitrogen-containing compound and a phosphorus flame retardant. However, these flame retardant polyamide resin compositions have excellent flame retardant properties, but cannot exhibit the expected properties because the strength decreases significantly due to the water absorption characteristic of the polyamide resin in an actual use environment. Further, when these flame retardant resin compositions are examined for surface mount type electric and electronic parts, polyamide 66 lacks heat resistance and polyamide 46 satisfies heat resistance, but the product is in the atmosphere during transportation and storage. In the surface mounting process, there is a problem that causes problems such as blistering of the product. Furthermore, molded articles formed from these flame-retardant polyamide resin compositions produce a large amount of bleeds derived from the triazine-based compounds contained in the resin composition on the surface in a high-temperature and high-humidity environment. For this reason, it has a problem of causing poor appearance of the product, does not satisfy the user needs, and has room for improvement.

  Patent Document 3 discloses a flame retardant resin composition that imparts high flame retardancy to polyamide 6, polyamide 66, and 6T polyamide by using a combination of a phosphinic acid metal salt, a phosphorous acid metal salt, and a triazine compound. Has been proposed. Although this patented technology seems to exert excellent effects on almost all polyamides including high melting point polyamides, a flame retardant containing a triazine compound is applied to high melting point polyamides represented by 6T polyamides. Sublimation and thermal decomposition occur due to insufficient heat resistance or purity of triazine compounds, which not only significantly reduces the appearance of molded products, but also accelerates the generation of bleed-out components derived from triazine compounds. The problem that a large amount of bleed material is generated on the surface of the molded body formed from the resin composition under actual use environment cannot be improved. Furthermore, 6T-based polyamide has a high saturated water absorption rate of 6%, and when applied to surface-mounted electrical and electronic parts, the above-mentioned blistering and water absorption cause a significant decrease in mechanical properties and dimensional changes, leading to stable product supply. I have a problem.

  As described above, the non-halogen flame retardant polyamide resins that have been proposed so far do not satisfy all of the high melting point, flame resistance, bleed-out resistance, and low water absorption. The fact is.

JP 2004-43647 A Japanese Patent No. 4454146 Japanese Patent No. 4951187

  The present invention was devised in view of the above-mentioned problems of the prior art, and its purpose is to provide a flame-retardant polyamide resin for electrical and electronic parts that is excellent in flame retardancy, bleed-out resistance, high melting point, and low water absorption. It is to provide a composition.

  In order to achieve the above object, the present inventor has excellent flame retardancy, generation of a bleed product on the surface of a molded product under an actual use environment such as high temperature and high humidity, a high melting point, and As a result of intensive investigations on the composition of the polyamide and the halogen-free flame retardant composition that greatly reduced the strength reduction due to water absorption, the present invention was completed.

That is, the present invention has the following configurations (1) to (4).
(1) Flame retardant polyamide resin composition containing 30-80 parts by mass of flame retardant combination (B) and 40-250 parts by mass of reinforcing material (C) with respect to 100 parts by mass of semi-aromatic polyamide resin (A) A flame retardant polyamide resin composition satisfying the following (a) to (d):
(A) Underwater equilibrium water absorption ≦ 3.0% of the polyamide resin composition
(B) The DSC melting peak temperature located on the lowest temperature side resulting from the polyamide resin of the polyamide resin composition is 290 ° C. to 350 ° C.
(C) A flame retardant combination (B) comprising a flame retardant (B-1) comprising a metal salt of phosphinic acid, a metal salt or a double salt containing phosphorous acid component and aluminum as constituent components (B-2) ) And a nitrogen-containing cyclic compound having an amino group. (D) Mass ratio of (B-1) component and (B-2) component of the flame retardant combination [(B-1) / ( B-2)] is 2.5 to 15
(2) The semi-aromatic polyamide resin (A) contains 50 mol% or more of a structural unit obtained from an equivalent molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid, and has 11 to 18 carbon atoms. The flame-retardant polyamide resin composition according to (1), which is obtained by copolymerizing one or more of aminocarboxylic acid or lactam.
(3) The semi-aromatic polyamide resin (A) contains 55 mol% or more of a structural unit obtained from an equivalent molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid, and has 11 to 18 carbon atoms. The flame-retardant polyamide resin composition according to (1), which is obtained by copolymerizing one or more of aminocarboxylic acid or lactam.
(4) 55-75 mol% of structural units obtained from (a) an equimolar molar salt of hexamethylenediamine and terephthalic acid, and (b) 11-aminoundecanoic acid or undecane. The flame-retardant polyamide resin composition according to any one of (1) to (3), which is a semi-aromatic polyamide resin having 45 to 25 mol% of a structural unit obtained from lactam as a structural component.
(5) 82-98 mol% of structural units obtained from the above-mentioned semi-aromatic polyamide resin (A) from (a ′) equimolar salt of decamethylenediamine and terephthalic acid, and (b ′) 11-aminoundecanoic acid Alternatively, the flame-retardant polyamide resin composition according to any one of (1) to (3), wherein the flame-retardant polyamide resin composition is a semi-aromatic polyamide resin containing 18 to 2 mol% of a structural unit obtained from undecane lactam. .
(6) The molded body formed using the polyamide resin composition is characterized in that no bleed product is produced on the surface of the molded body even after 200 hours in an environment of 80 ° C. and 85% RH ( The flame-retardant polyamide resin composition according to any one of 1) to (5).

  The flame-retardant polyamide resin composition of the present invention has a high melting point and not only provides excellent flame retardancy and mechanical strength by using a specific non-halogen flame retardant, but also an actual use environment such as high temperature and high humidity. The generation of bleeds on the surface of the molded product can be suppressed below, and further, the strength reduction and dimensional change caused by the water absorption of the polyamide resin can be reduced, and a product satisfying user needs can be manufactured. .

  The polyamide resin composition of the present invention is intended to be used for electrical and electronic parts mounted on electrical and electronic equipment and automobiles, and housings of electrical equipment. Specific examples include connectors, switches, IC and LED housings, sockets, relays, resistors, capacitors, coil bobbins, and various housing parts. The polyamide resin composition of the present invention includes all these products. It can be manufactured by injection molding.

The semi-aromatic polyamide resin (A) used in the present invention is not particularly limited, and the semi-aromatic polyamide having an acid amide bond (—CONH—) in the molecule and an aromatic ring (benzene ring). It is.
Specific semi-aromatic polyamides include 6T polyamides (for example, polyamide 6T / 6I made of terephthalic acid / isophthalic acid / hexamethylenediamine, polyamide 6T / 66 made of terephthalic acid / adipic acid / hexamethylenediamine, terephthalic acid / Isophthalic acid / adipic acid / polyamide 6T / 6I / 66 composed of hexamethylenediamine, terephthalic acid / hexamethylenediamine / 2-methyl-1, polyamide 6T / M-5T composed of 5-pentamethylenediamine, terephthalic acid / hexa Polyamide 6T / 6 composed of methylenediamine / ε-caprolactam, Polyamide 6T / 4T composed of terephthalic acid / hexamethylenediamine / tetramethylenediamine, 9T polyamide (terephthalic acid / 1,9-nonanediamine / 2) Polyamide comprising methyl-1,8-octanediamine), 10T polyamide (terephthalic acid / 1,10-decanediamine), 12T polyamide (terephthalic acid / 1,12-dodecanediamine), sebacic acid / paraxylenediamine Etc.

  Since the polyamide resin composition of the present invention is required to correspond to the surface mounting technology which is a general production method in electrical and electronic component applications, the melting point measured by the method described in the section below is 290 to 290. It must be 350 ° C. In addition, melting | fusing point is a melting peak temperature measured by DSC (differential scanning calorimeter) located in the lowest temperature side resulting from the polyamide resin of a polyamide resin composition here. Moreover, it is preferable that melting | fusing point is 300 to 340 degreeC, and it is more preferable that it is 310 to 340 degreeC. When the melting point exceeds the above upper limit, the processing temperature required for injection molding the polyamide resin composition of the present invention becomes extremely high, so that the polyamide resin composition is thermally decomposed and the desired performance and appearance cannot be obtained. It is possible and not preferred. Moreover, when melting | fusing point is less than the said minimum, the heat resistance in a surface mounting process (230-280 degreeC) will run short, and it may produce defects, such as a product deformation | transformation in a process, and is unpreferable.

  The polyamide resin composition of the present invention is required to correspond to the surface mounting process, and the strength and product dimensions after the product absorbs water in the actual use environment due to the miniaturization and structural densification of the electrical and electronic parts. Is required to be stably maintained. Therefore, it is necessary that the underwater equilibrium water absorption measured by the method described in the Examples section below satisfies 3.0% or less. Further, the equilibrium water absorption rate in water is preferably 2.5% or less. The lower limit of the equilibrium water absorption rate in water is preferably 0%, but is preferably about 1.5% in view of the characteristics of the semi-aromatic polyamide (A) used in the present invention. If the underwater equilibrium water absorption rate exceeds the above upper limit, strength reduction due to water absorption and dimensional change become remarkable, which may cause problems such as insufficient strength of the product and defective assembly, which is not preferable.

Among the semi-aromatic polyamides, the semi-aromatic polyamide resin (A) used in the present invention is preferably the following semi-aromatic polyamide resin (A) from the viewpoints of melting point and water equilibrium water absorption.
The semi-aromatic polyamide resin (A) contains 50 mol% or more of a structural unit obtained from an equivalent molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid, and an aminocarboxylic acid having 11 to 18 carbon atoms or A semi-aromatic polyamide resin obtained by copolymerizing one or a plurality of lactams is preferable. The structural unit obtained from an equimolar molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid is 50 to 98 mol%, and one or more of 11 to 18 aminocarboxylic acids or lactams are 2 to 50. More preferably, it is mol%.

As a C2-C12 diamine component which comprises a semi-aromatic polyamide resin (A), a C2-C12 aliphatic diamine is preferable.
Examples of the diamine component having 2 to 12 carbon atoms constituting the semi-aromatic polyamide resin (A) include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, and 1,5-pentamethylene. Diamine, 2-methyl-1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl- 1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine can be mentioned, and these can be used alone or in combination.
In the case of a semi-aromatic polyamide comprising a structural unit obtained from an equimolar molar salt of a diamine having 9 or more carbon atoms and terephthalic acid, since it may have a melting point at 290 ° C. or lower, a diamine having 2 to 8 carbon atoms and A polyamide resin containing 50 mol% or more of a structural unit obtained from an equivalent molar salt with terephthalic acid and having a melting point on the lowest temperature side of 290 ° C. or more is one preferred embodiment. When the structural unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid is less than 50 mol%, the crystallinity and mechanical properties may be lowered.
Further, in the case of a semi-aromatic polyamide comprising a structural unit obtained from an equimolar molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid, the melting point on the lowest temperature side is contained by including 55 mol% or more of this structural unit. It is also possible to use a polyamide resin having a temperature of 290 ° C. or higher, which is a preferred embodiment. The structural unit obtained from an equimolar molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid is 55 to 98 mol%, and one or more of 11 to 18 aminocarboxylic acids or lactams are 2 to 45. More preferably, it is mol%. When the structural unit obtained from an equimolar molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid is less than 55 mol%, crystallinity and mechanical properties may be deteriorated.

  The semi-aromatic polyamide resin (A) can be copolymerized with other components at 50% mol or less in the structural unit. Examples of the copolymerizable diamine component include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4)- Alicyclic diamines such as aliphatic diamines such as trimethylhexamethylenediamine, piperazine, cyclohexanediamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4′-aminocyclohexyl) methane, isophoronediamine Examples thereof include aromatic diamines such as diamine, metaxylylenediamine, paraxylylenediamine, paraphenylenediamine and metaphenylenediamine, and hydrogenated products thereof.

Examples of copolymerizable acid components include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, 4 , 4′-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid, 5-hydroxyisophthalic acid and other aromatic dicarboxylic acids, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1 , 11-Undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2 -Cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer Aliphatic and alicyclic dicarboxylic acids such as acid.
Examples of copolymerizable components include lactams such as ε-caprolactam, 11-aminoundecanoic acid, undecane lactam, 12-aminododecanoic acid, and 12-lauryllactam, and aminocarboxylic acids having a structure in which they are ring-opened. It is done.

  Among the above components, the copolymer component is preferably a copolymer of one or more of an aminocarboxylic acid having 11 to 18 carbon atoms or a lactam having 11 to 18 carbon atoms.

  When the copolymer component is composed of dicarboxylic acid and diamine, the melting point is less than 290 ° C. depending on the combination, which is not preferable. The aminocarboxylic acid or lactam having 11 to 18 carbon atoms plays a role of adjusting the melting point and the crystallization temperature to improve the moldability, and reducing the water absorption rate to improve trouble caused by changes in physical properties and dimensional changes during water absorption. And, by introducing a flexible skeleton, it has a role of improving fluidity at the time of melting.

  The semi-aromatic polyamide resin (A) used in the present invention comprises (a) 55 to 75 mol% of a structural unit obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, and (b) 11-aminoundecanoic acid. Or it is especially preferable that it is a semi-aromatic polyamide resin which has 45-25 mol% of structural units obtained from undecane lactam as a structural component. At this time, the semi-aromatic polyamide resin (A) includes, as a constituent component, a constituent unit composed of the above-described copolymerizable components other than the constituent unit of (a) and the constituent unit of (b) at a ratio of 20 mol% or less. Also good. By using the semi-aromatic polyamide (A) comprising this constituent component, it becomes possible to realize excellent moldability in addition to high melting point, low water absorption and high fluidity.

  Such a semi-aromatic polyamide resin (A) is blended in order to realize excellent moldability in addition to high heat resistance, fluidity and low water absorption, and includes a component (a) corresponding to 6T polyamide. (B) component corresponding to 11 polyamide in a specific ratio, and a conventional 6T polyamide (for example, polyamide 6T / 6I composed of terephthalic acid / isophthalic acid / hexamethylenediamine, terephthalic acid / adipic acid / Polyamide 6T / 66 composed of terephthalic acid, Polyamide 6T / 6I / 66 composed of terephthalic acid / isophthalic acid / adipic acid / hexamethylenediamine, terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine Polyamide 6T / M-5T, terephthalic acid / hexamethylenediamine / ε-ca It has a feature that superabsorbent which is a disadvantage of polyamide 6T / 6) consisting Rorakutamu is greatly improved. Furthermore, since it has a flexible long-chain fatty skeleton derived from 11 polyamide components, it also has a feature that it is easy to ensure fluidity.

  The component (a) corresponds to 6T polyamide obtained by co-condensation polymerization of hexamethylenediamine (6) and terephthalic acid (T) in an equimolar amount, and specifically, the following formula (I) It is represented by

  The component (a) is a main component of the semi-aromatic polyamide resin (A) and has a role of imparting excellent heat resistance, mechanical properties, slidability, and the like to the semi-aromatic polyamide resin (A). The blending ratio of the component (a) in the semi-aromatic polyamide resin (A) is preferably 55 to 75 mol%, more preferably 60 to 70 mol%, still more preferably 62 to 68 mol%. When the blending ratio of the component (a) is less than the above lower limit, the 6T polyamide, which is a crystal component, may be subjected to crystal inhibition by the copolymer component, leading to deterioration of moldability and high temperature characteristics, while exceeding the above upper limit. The melting point becomes too high and may decompose during processing.

  The component (b) corresponds to 11 polyamide obtained by polycondensation of 11-aminoundecanoic acid or undecane lactam, and is specifically represented by the following formula (II).

  The component (b) is for improving water absorption and fluidity, which is a drawback of the component (a). The moldability is adjusted by adjusting the melting point and the temperature rising crystallization temperature of the semi-aromatic polyamide resin (A). It has a role of improving the fluidity at the time of melting by introducing a flexible skeleton and a role of improving the trouble due to a change in physical properties and dimensional change at the time of water absorption by reducing the water absorption rate. The blending ratio of the component (b) in the semi-aromatic polyamide resin (A) is preferably 45 to 25 mol%, more preferably 40 to 30 mol%, still more preferably 38 to 32 mol%. When the blending ratio of the component (b) is less than the lower limit, the melting point of the semi-aromatic polyamide (A) is not sufficiently lowered, the moldability may be insufficient, and the water absorption rate of the obtained resin is reduced. The effect is insufficient, and there is a possibility that instability such as a decrease in mechanical properties and a dimensional change during water absorption occurs. When the above upper limit is exceeded, the melting point of the semi-aromatic polyamide resin is too low, the crystallization rate is slow, the moldability may be adversely affected, and the amount of the component (a) corresponding to 6T polyamide is small. Therefore, the mechanical properties and heat resistance may be insufficient.

The semi-aromatic polyamide resin (A) used in the present invention comprises (a ′) 82 to 98 mol% of a structural unit obtained from an equimolar molar salt of decamethylenediamine and terephthalic acid, and (b ′) 11. -A semi-aromatic polyamide resin having, as a constituent, 18 to 2 mol% of a structural unit obtained from aminoundecanoic acid or undecane lactam is particularly preferable. At this time, the semi-aromatic polyamide resin (A) comprises a constituent unit composed of the above-described copolymerizable components other than the constituent unit (a ′) and the constituent unit (b ′) in a proportion of 15 mol% or less. It is good as an ingredient. By using the aromatic polyamide (A) comprising this constituent component, it becomes possible to realize excellent moldability in addition to high melting point, low water absorption, and high fluidity.
The component (a ′) is used for the same purpose as the component (a) and the component (b ′) is basically the same as the component (b). The component (a ′) uses a longer-chain diamine than the component (a), and partly combines the function of the component (b). Therefore, the preferable blending ratio of the component (a ′) is more than the component (a). growing.

  Examples of the catalyst used when producing the semi-aromatic polyamide resin (A) include phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt, ammonium salt, and ester thereof. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. Examples of the ester include ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, and phenyl ester. Moreover, it is preferable to add alkali compounds, such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, from a viewpoint of melt retention stability improvement.

  The relative viscosity (RV) measured at 20 ° C. in 96% concentrated sulfuric acid of the semi-aromatic polyamide resin (A) is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and further Preferably it is 1.5-2.5. Examples of a method for setting the relative viscosity of the polyamide within a certain range include a means for adjusting the molecular weight.

  The semi-aromatic polyamide resin (A) adjusts the amount of end groups and the molecular weight of the polyamide by adjusting the molar ratio between the amount of amino groups and the amount of carboxyl groups and by polycondensation or by adding a terminal blocking agent. be able to. When polycondensation is performed at a fixed ratio of the amino group amount and the carboxyl group amount, the molar ratio of diamine to dicarboxylic acid (diamine / dicarboxylic acid) used is changed from 1.00 / 1.05 to 1. It is preferable to adjust to the range of 10 / 1.00.

  Examples of the timing for adding the end-capping agent include raw material charging, polymerization initiation, polymerization late, or polymerization termination. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but acid anhydrides such as monocarboxylic acid or monoamine, phthalic anhydride, Monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can be used. Examples of the end capping agent include aliphatic monoacids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Alicyclic monocarboxylic acids such as carboxylic acid and cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids, maleic anhydride Acid, phthalic anhydride, acid anhydrides such as hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. Aliphatic monoamines, Examples thereof include alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.

  The acid value and amine value of the semi-aromatic polyamide resin (A) are preferably 0 to 200 eq / ton and 0 to 100 eq / ton, respectively. When the terminal functional group exceeds 200 eq / ton, not only gelation and deterioration are promoted during the melt residence, but also problems such as coloring and hydrolysis are caused even in the use environment. On the other hand, when a reactive compound such as glass fiber or maleic acid-modified polyolefin is compounded, it is preferable that the acid value and / or the amine value be 5 to 100 eq / ton in accordance with the reactivity and the reactive group.

  The semi-aromatic polyamide resin (A) can be produced by a conventionally known method, and can be easily synthesized, for example, by co-condensing a raw material monomer. The order of the copolycondensation reaction is not particularly limited, and all the raw material monomers may be reacted at once, or a part of the raw material monomers may be reacted first, followed by the remaining raw material monomers. Although the polymerization method is not particularly limited, the process from raw material preparation to polymer production may proceed in a continuous process. After the oligomer is produced once, the polymerization is advanced by an extruder or the like in another process, or the oligomer is solidified. A method of increasing the molecular weight by phase polymerization may be used. By adjusting the charging ratio of the raw material monomer, the proportion of each structural unit in the copolymerized polyamide to be synthesized can be controlled.

  The semi-aromatic polyamide resin (A) is preferably present in a proportion of 20 to 70% by mass, more preferably 25 to 55% by mass in the polyamide resin composition of the present invention. When the ratio of the semi-aromatic polyamide resin (A) is less than the above lower limit, the mechanical strength becomes low, and when it exceeds the upper limit, the flame retardants (B-1) and (B-2) and the reinforcing material (C) Therefore, the desired effect is hardly obtained.

  The flame retardant (B-1) is blended for imparting flame retardancy to the molded body formed of the polyamide resin of the present invention. For example, the phosphinate and / or diphosphinate and / or These polymers are mentioned. Specific examples include aluminum salts, calcium salts, and zinc salts of methylethylphosphinic acid, aluminum salts, calcium salts, and zinc salts of diethylphosphinic acid, and aluminum salts, calcium salts, and zinc salts of methylpropylphosphinic acid. . In particular, an aluminum salt is preferable from the viewpoint of stability.

  Flame retardant (B-2) is composed of phosphorous acid component, alkaline earth metal (Mg, Ca, Sr, Ba), transition metal (Ti, Mn, Fe, Ni, Cu, Zr, Zn, Mo, Pb, W) , Etc.), and a metal salt or a double salt containing aluminum as a constituent component, and is combined with the flame retardant (B-1) in order to express high flame retardancy. In particular, a metal salt mainly composed of an aluminum phosphite salt is preferable in terms of stability and the effects of the present invention. The aluminum phosphite may be foamable. The phosphorous acid metal salt or double salt mentioned here is an illustration, and is not limited to these.

The ratio of the total compounding quantity of a flame retardant (B-1) and (B-2) is 30-80 mass parts with respect to 100 mass parts of polyamide resins (A). Moreover, 35-75 mass parts is preferable, and 40-70 mass parts is more preferable. If the total blending amount of the flame retardants (B-1) and (B-2) is less than the above lower limit, the target advanced flame retardancy cannot be obtained, and if the above upper limit is exceeded, the physical properties may be greatly reduced. The continuous productivity at the time of compounding may be lowered, which is not preferable.
In particular, when the semi-aromatic polyamide resin (A) selected from the viewpoints of the melting point and the equilibrium water absorption rate in water is used, the blending amount is important in order to obtain high flame retardancy.

  The blending mass ratio [(B-1) / (B-2)] of the flame retardants (B-1) and (B-2) is important for coexisting advanced flame retardancy and mechanical properties, (B-1) / (B-2)] needs to be in the range of 2.5-15. [(B-1) / (B-2)] is preferably 2.8 to 13, and more preferably 3.0 to 11. When the blending mass ratio [(B-1) / (B-2)] of the flame retardant is out of the above range, the target high flame retardancy may not be obtained, which is not preferable.

  The combination of flame retardants (B-1) and (B-2) is important for obtaining a resin composition having the high melting point, low water absorption, high flame retardancy, and bleed-out resistance, which is the object of the present invention. It is. In particular, high flame retardancy can be exhibited without using nitrogen-containing cyclic compounds having amino groups that have been generally used to obtain high flame retardancy, and high temperature and high humidity. In an actual use environment such as the above, it becomes possible to suppress the bleed product on the product surface, so that a product that can be used stably without being influenced by the use environment can be supplied. The flame-retardant polyamide resin composition of the present invention, when using the specific semi-aromatic polyamide resin (A), without using a nitrogen-containing cyclic compound having an amino group widely used as a flame retardant, A major point of the invention is that it has high flame retardancy and can suppress the bleed product on the product surface under actual use environment such as high temperature and high humidity.

  The reinforcing material (C) is blended to improve the moldability of the polyamide resin composition and the strength of the molded product, and uses at least one selected from a fibrous reinforcing material and a needle-shaped reinforcing material. It is preferable. Examples of the fibrous reinforcing material include glass fiber, carbon fiber, boron fiber, ceramic fiber, and metal fiber. Examples of the acicular reinforcing material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, and carbonic acid. Calcium whiskers, magnesium sulfate whiskers, wollastonite and the like can be mentioned. As the glass fiber, chopped strands or continuous filament fibers having a length of 0.1 mm to 100 mm can be used. As the cross-sectional shape of the glass fiber, a glass fiber having a circular cross section and a non-circular cross section can be used. The diameter of the circular cross-section glass fiber is 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less. Further, a glass fiber having a non-circular cross section is preferred from the viewpoint of physical properties and fluidity. Non-circular cross-sectional glass fibers include those that are substantially oval, substantially oval, and substantially bowl-shaped in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8. It is preferable. Here, the flatness is assumed to be a rectangle with the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of the rectangle is the major axis, and the length of the short side is the minor axis. It is the ratio of major axis / minor axis. The thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 μm and the major axis is about 2 to 100 μm. Moreover, the glass fiber becomes a fiber bundle, and the thing of the chopped strand shape cut | disconnected by about 1-20 mm of fiber length can use it preferably. In order to improve the affinity with the polyamide resin, the fibrous reinforcing material is preferably treated with an organic treatment or a coupling agent, or used in combination with a coupling agent at the time of melt compounding. Any of a coupling agent, a titanate coupling agent, and an aluminum coupling agent may be used. Among them, an aminosilane coupling agent and an epoxysilane coupling agent are particularly preferable.

  The ratio of the reinforcing material (C) is necessary for 40 to 250 parts by mass with respect to 100 parts by mass of the polyamide resin (A) to sufficiently exhibit the mechanical properties. Moreover, 50-220 mass parts is preferable, and 60-200 mass parts is more preferable. When the ratio of the reinforcing material (C) is less than the above lower limit, the mechanical strength of the molded product is lowered, and when it exceeds the above upper limit, the extrudability and the moldability may be lowered.

  In the polyamide resin composition of the present invention, various additives of conventional polyamide resin compositions for electric and electronic parts can be used. Additives include stabilizers, impact modifiers, release agents, slidability improvers, colorants, plasticizers, crystal nucleating agents, polyamides other than semi-aromatic polyamide resins (A), and thermoplastics other than polyamides Resin etc. are mentioned. The possible blending amounts of these components in the polyamide resin composition are as described below, but the total of these components is preferably 30% by mass or less, more preferably 20% by mass or less in the polyamide resin composition. 10 mass% or less is further more preferable, and 5 mass% or less is especially preferable.

  Stabilizers include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and copper compounds. Copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate, and copper acetate can be used. Further, as a component other than the copper compound, an alkali metal halide compound is preferably contained. Examples of the alkali metal halide compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, bromide. Examples thereof include sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like. These additives may be used alone or in combination of several kinds. An optimum amount of the stabilizer may be selected, but a maximum of 5 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A).

  The polyamide resin composition of the present invention may be polymer blended with a polyamide having a composition different from that of the semi-aromatic polyamide resin (A). The polyamide having a composition different from that of the semi-aromatic polyamide resin (A) of the present invention is not particularly limited, but polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), poly Tetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polymetaxylylene adipamide (polyamide MXD6), polyparaxylylene adipamide (polyamide PXD6), polytetramethylene sebacamide (Polyamide 410), polyhexamethylene sebamide (polyamide 610), polydecamethylene adipamide (polyamide 106), polydecamethylene sebamide (polyamide 1010), polyhexamethylene dodecamide (polyamide 612), polydeca Methylenede Camide (polyamide 1012), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polytetramethylene terephthalamide (polyamide 4T), polypentamethylene terephthalamide (polyamide 5T), poly-2- Methyl pentamethylene terephthalamide (polyamide M-5T), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), poly 2-methyl-octamethylene terephthalamide, polynonamethylene terephthalamide (polyamide 9T), polydecamethylene Terephthalamide (polyamide 10T), polyundecamethylene terephthalamide (polyamide 11T), polydodecamethylene terephthalamide (polyamide 12T), polybis 3-methyl-4-aminohexyl) methane terephthalamide (polyamide PACMT), polybis (3-methyl-4-aminohexyl) methane isophthalamide (polyamide PACMI), polybis (3-methyl-4-aminohexyl) methane dodecamide (Polyamide PACM12), polybis (3-methyl-4-aminohexyl) methanetetradecanamide (polyamide PACM14), polyalkyl ether copolymerized polyamide or the like, or these copolymerized polyamides are used alone or in combination of two or more. May be. Among these, polyamide 66, polyamide 6T / 66, etc. may be blended with polyamide 10T derivatives for imparting further low water absorption, etc., in order to increase the crystallization speed and improve the moldability. The addition amount of the polyamide having a composition different from that of the semi-aromatic polyamide resin (A) may be selected, but a maximum of 50 parts by mass is added to 100 parts by mass of the semi-aromatic polyamide resin (A). It is possible.

  A thermoplastic resin other than polyamide having a composition different from that of the semi-aromatic polyamide resin (A) may be added to the polyamide resin composition of the present invention. Polymers other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyether sulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene Phthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene ( S), polymethyl methacrylate, acrylonitrile - styrene copolymer (AS), acrylonitrile - butadiene - styrene copolymer (ABS) and the like. These thermoplastic resins can be blended in a molten state by melt kneading. However, the thermoplastic resin may be made into a fiber or particle and dispersed in the polyamide resin composition of the present invention. An optimum amount of the thermoplastic resin may be selected, but a maximum of 50 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A).

  As the impact modifier, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene- Polyolefin resins such as methacrylic acid ester copolymer, ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -Polytetramethylene glycol, polycaprolactone, or poly (polyethylene glycol) as a hard segment made of vinyl polymer resin such as styrene copolymer (SIS), acrylate copolymer, polybutylene terephthalate or polybutylene naphthalate. Polyester block copolymer in which the ball sulfonate diol as a soft segment, a polyamide elastomer, urethane elastomer, acrylic elastomer, silicone rubber, fluorinated rubber, and the like polymer particles having a core-shell structure constituted from two different polymers. An optimum amount of the impact modifier may be selected, but a maximum of 30 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A).

  When a thermoplastic resin other than the semi-aromatic polyamide resin (A) and an impact resistance improving material are added to the polyamide resin composition of the present invention, a reactive group capable of reacting with the polyamide is copolymerized. The reactive group is a group capable of reacting with an amino group, a carboxyl group and a main chain amide group which are terminal groups of the polyamide resin. Specific examples include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, an isocyanate group, etc. Among them, an acid anhydride group is most excellent in reactivity. There is also a report that the thermoplastic resin having a reactive group that reacts with the polyamide resin is finely dispersed in the polyamide and is finely dispersed, so that the distance between the particles is shortened and the impact resistance is greatly improved [ S, Wu: Polymer 26, 1855 (1985)].

  Examples of the release agent include long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicone, polyethylene oxide, and the like. The long chain fatty acid preferably has 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. Or a metal salt may be formed. Examples of the amide compound include ethylene bisterephthalamide and methylene bisstearyl amide. These release agents may be used alone or as a mixture. An optimum amount of the release material may be selected, but a maximum of 5 parts by mass can be added to 100 parts by mass of the semi-aromatic polyamide resin (A).

  The flame retardant polyamide resin composition of the present invention is not only capable of imparting excellent flame retardancy by optimizing the flame retardant combination, but is also a molded product in an actual use environment as seen in conventional flame retardant combinations. It is possible to suppress surface bleed generation at a high level. Furthermore, by using the semi-aromatic polyamide resin (A) characterized by a melting point of 290 ° C. to 350 ° C. and an equilibrium water absorption ≦ 3.0% in water, it has a high melting point in addition to high flame retardancy. In addition, it is possible to obtain a flame retardant polyamide resin composition having excellent characteristics such as a decrease in mechanical characteristics and suppression of dimensional changes during water absorption, and it is possible to supply a product that highly satisfies user needs.

  The polyamide resin composition of this invention can be manufactured by mix | blending each above-mentioned component with a conventionally well-known method. For example, each component is added during the polycondensation reaction of the semiaromatic polyamide resin (A), the semiaromatic polyamide resin (A) and other components are dry blended, or a twin screw type extruder is used. Examples thereof include a method of melting and kneading each constituent component.

The polyamide resin composition of the present invention can be molded by a conventionally known method such as extrusion molding, injection molding or compression molding. The formed molded body is excellent in flame retardancy and processability, and can be used for various applications. Specific examples include various electrical and electronic parts such as connectors and switches, and housing parts, but are not limited thereto.
The molded body formed using the polyamide resin composition of the present invention is characterized in that no bleed product is produced on the surface of the molded body even after 200 hours have passed in an environment of 80 ° C. and 85% RH.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measured value described in the Example is measured by the following method.

(1) Relative viscosity 0.25 g of polyamide resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C. using an Ostwald viscometer.

(2) Melting point (Tm)
Using an injection molding machine EC-100 manufactured by Toshiba Machine, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 35 ° C., the length 127 mm, the width 12.6 mm, and the thickness 0.8 mmt. A piece was injection molded to produce a test piece. In order to measure the melting point (Tm) of the obtained molded product, 5 mg of a part of the molded product was weighed into an aluminum pan, sealed with an aluminum lid, a measurement sample was prepared, and then a differential scanning calorimeter Using SEIKO INSTRUMENTS SSC / 5200, the temperature was raised from room temperature to 20 ° C./min in a nitrogen atmosphere, and the measurement was performed up to the melting point of the resin + 30 ° C. At that time, the peak top temperature observed on the lowest temperature side among the endothermic peaks obtained by melting was defined as the melting point (Tm).

(3) Underwater equilibrium water absorption rate Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C, the mold temperature is set to 135 ° C, and a flat plate with a length of 100 mm, a width of 100 mm, and a thickness of 1 mm is injected. Molded to prepare a test piece for evaluation. This test piece was annealed in an atmosphere of 140 ° C. for 2 hours, and then the weight was measured. The weight at this time was taken as the weight at the time of drying. Furthermore, after the annealed test piece was immersed in 80 ° C. hot water for 50 hours, the weight was measured, and the weight at this time was defined as the weight at the time of saturated water absorption. The underwater equilibrium water absorption was determined from the following equation from the saturated water absorption and dry weights measured by the method described above.
Equilibrium water absorption rate (%) in water = {(weight at saturated water absorption−weight at drying) / weight at drying} × 100

(4) Bending strength retention during water absorption Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 135 ° C., and conforms to ISO 294-1 for evaluation. A test piece was prepared. The produced test piece was annealed in an atmosphere of 140 ° C. for 2 hours, and then a part of the test piece was used to evaluate bending properties in accordance with ISO 178. Further, the remaining test piece after the annealing treatment was allowed to stand in an atmosphere of 85 ° C. and 85% RH (relative humidity) for 1000 hours, and then evaluated for bending properties in accordance with ISO 178. The bending strength retention at the time of water absorption was determined from the following formula from the bending strength after annealing and after saturated water absorption.
Bending strength retention rate during water absorption (%) = (bending strength after saturated water absorption / bending strength after annealing) × 100

(5) Bending strength during drying Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 135 ° C., and an evaluation test piece according to ISO 294-1. Was made. Bending physical property evaluation was performed based on ISO 178 using the prepared test piece. The bending strength was determined according to the following criteria.
○: Bending strength during drying ≧ 170 MPa
X: Bending strength during drying <170 MPa

(6) Flame retardance Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 135 ° C., the length is 127 mm, the width is 12.7 mm, and the thickness is 1.6 mm. Test specimens for evaluation were produced by injection molding. Using this test piece, flame retardancy evaluation was performed based on the UL-94 vertical combustion test.

(7) Bleed-out resistance Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 135 ° C., and a flat plate of length 100 × width 100 × thickness 1 mm is injected. Molded to create a test specimen for evaluation. The test specimen for evaluation was allowed to stand in an atmosphere of 80 ° C. and 85% RH (relative humidity) for 200 hours, and then the state of generation of bleeds on the surface of the test specimen was visually confirmed according to the following criteria.
○: No bleed material generated ×: Bleeded material generated

  This example was carried out using a semi-aromatic polyamide resin (A) synthesized as exemplified below.

<Synthesis Example 1>
7.54 kg of 1,6-hexamethylenediamine, 10.79 kg of terephthalic acid, 7.04 kg of 11-aminoundecanoic acid, 9 g of sodium hypophosphite as a catalyst, 40 g of acetic acid as a terminal conditioner and 17.52 kg of ion-exchanged water The mixture was charged into a liter autoclave, pressurized with N ₂ from normal pressure to 0.05 MPa, released, and returned to normal pressure. This operation was performed 3 times, N ₂ substitution was performed, and then uniform dissolution was performed at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, heated to 240 ° C. with a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Thereafter, this low-order condensate is directly supplied to a twin-screw extruder (screw diameter: 37 mm, L / D = 60) while maintaining the molten state, and the resin temperature is 335 ° C. while water is removed from three vents. The polycondensation proceeded under melting to obtain a semi-aromatic polyamide resin (A). The obtained semi-aromatic polyamide resin (A) had a relative viscosity of 2.1 and a melting point of 314 ° C. The constituent monomer ratios of the semi-aromatic polyamide resin (A) of Synthesis Example 1 are shown in Table 1.

<Synthesis Example 2>
The amount of 1,6-hexamethylenediamine was changed to 8.12 kg, the amount of terephthalic acid was changed to 9.96 kg, the amount of 11-aminoundecanoic acid was changed to 6.03 kg, and adipic acid (other than terephthalic acid) The dicarboxylic acid (1.46 kg) was charged, and the resin temperature of the twin screw extruder was changed to 330 ° C. Except for these, the semi-aromatic polyamide resin (A) was synthesized in the same manner as in Synthesis Example 1. The obtained semi-aromatic polyamide resin (A) had a relative viscosity of 2.1 and a melting point of 310 ° C. The constituent monomer ratios of the semi-aromatic polyamide resin (A) of Synthesis Example 2 are shown in Table 1.

<Synthesis Example 3>
7.04 kg of 11-aminoundecanoic acid was changed to 6.41 kg of undecane lactam, and the resin temperature of the twin screw extruder was changed to 335 ° C. Except for these, the semi-aromatic polyamide resin (A) was synthesized in the same manner as in Synthesis Example 1. The obtained semi-aromatic polyamide resin (A) had a relative viscosity of 2.1 and a melting point of 315 ° C. Table 1 shows the constituent monomer ratios of the semi-aromatic polyamide resin (A) in Synthesis Example 3.

<Synthesis Example 4>
50 mg of 15.10 kg of 1,10-decamethylenediamine, 14.95 kg of terephthalic acid, 2.01 kg of 11-aminoundecanoic acid, 9 g of sodium hypophosphite as a catalyst, 40 g of acetic acid as a terminal adjuster and 17.52 kg of ion-exchanged water A semi-aromatic polyamide resin (A) was synthesized in the same manner as in Synthesis Example 1 in a liter autoclave. The obtained semi-aromatic polyamide resin (A) had 10T / 11 = 90/10 (molar ratio), a relative viscosity of 2.0, and a melting point of 304 ° C.

<Synthesis Example 5>
According to the method described in Example 1 of the re-published patent WO06 / 112300, a terephthalic acid unit, an adipic acid unit, and a 1,6-hexamethylenediamine unit (terephthalic acid unit: adipic acid unit molar ratio is 63: A comparative semi-aromatic polyamide resin comprising 37) was synthesized. The obtained semi-aromatic polyamide resin (A) had a relative viscosity of 2.1 and a melting point of 320 ° C. The constituent monomer ratios of the comparative semi-aromatic polyamide resin (A) are shown in Table 1.

Examples 1-6, Comparative Examples 1-11
In the components and mass ratios (parts by mass) described in Tables 2 and 3, melt kneading was performed at a melting point of each polyamide raw material + 20 ° C. using a twin screw extruder STS-35 manufactured by Coperion Co., Ltd., Examples 1 to 6, Polyamide resin compositions of Comparative Examples 1 to 11 were obtained. The raw materials used in the preparation of the polyamide resin composition are as follows. The release agent and stabilizer used as other additives were used in a mass ratio of 1: 5.
Polyamide raw material: Semi-aromatic polyamide resin (A) produced based on Synthesis Examples 1 to 5, PA6T / 6 (polyamide 6T / 6) (Ultramide (registered trademark) KR4351 manufactured by BASF)
Flame retardant (B-1): diethylphosphinic acid aluminum salt (EXOLIT (registered trademark) OP1230 manufactured by Clariant Japan)
Flame retardant (B-2): Aluminum phosphite (APA-100 manufactured by Taihei Chemical Industrial Co., Ltd.)
Flame retardant: Melamine polyphosphate (MELAPUR (registered trademark) 200/70 manufactured by BASF)
Reinforcing material (C): Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., T-275H)
Mold release agent: Magnesium stearate Stabilizer: Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Chiba Specialty Chemicals)

  As is clear from Table 2, in Examples 1 to 6, not only satisfying the flame retardancy (flame retardancy is V-0), but also the bending strength during drying is a value sufficient to maintain the strength as a product. (170 MPa or more), very high bending strength retention at the time of water absorption, exhibit stable characteristics even in high-temperature and high-humidity usage environments, and satisfy excellent bleed-out resistance. You can see that On the other hand, as apparent from Table 3, in Comparative Examples 1 to 3, the blending balance of the flame retardants (B-1) and (B-2) is not optimal, and sufficient flame retardancy can be exhibited. Can not. In Comparative Example 4, flame retardancy, low water absorption, bending strength retention at water absorption, and bleed-out resistance are satisfied, but since the amount of flame retardant is excessive, the bending strength at drying is significantly reduced. It cannot be used as a product. In Comparative Examples 5 and 6, although flame retardancy and bleed-out resistance are satisfied, the bending strength retention rate at the time of water absorption is low, and the characteristics cannot be stably exhibited depending on the use environment conditions, which may lead to product defects. There is. In Comparative Example 7, melamine polyphosphate is included in the flame retardant combination of the example, and although it satisfies the flame retardancy, the bending strength at the time of drying, the bending strength retention at the time of water absorption, etc., the product is inferior in the bleed-out resistance. It may cause poor appearance when used. In Comparative Example 8, although the flame retardant combination is changed to a combination of the flame retardant (B-1) and melamine polyphosphate, stable flame retardancy can be exhibited in the same manner as in the examples, but the bleed-out resistance is poor. It may cause appearance defects when using the product. In Comparative Examples 9 and 10, although stable flame retardancy can be exhibited as in Comparative Example 8, the bending strength retention at the time of water absorption is low and the bleed-out resistance is poor, so cracks and poor appearance due to insufficient product strength May cause. In Comparative Example 11, only the flame retardant (B-1) is blended, and sufficient flame retardancy cannot be exhibited.

  The flame retardant polyamide resin composition of the present invention can not only exhibit excellent flame retardancy and strength by using a specific non-halogen flame retardant combination in an optimum blending amount, but also can be used in actual use such as high temperature and high humidity. In the environment, the generation of bleeds on the surface of the molded product can be suppressed, and further, the strength reduction and dimensional change caused by water absorption of the polyamide resin can be reduced. It can be produced advantageously.

Claims (5)

A flame retardant polyamide resin composition containing 30 to 80 parts by mass of a flame retardant combination (B) and 40 to 250 parts by mass of a reinforcing material (C) with respect to 100 parts by mass of a semi-aromatic polyamide resin (A). The semi-aromatic polyamide resin (A) contains 50 mol% or more of a structural unit obtained from an equimolar molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid, and an aminocarboxylic acid having 11 to 18 carbon atoms. A flame retardant polyamide resin composition, which is a semi-aromatic polyamide resin obtained by copolymerizing one or a plurality of acids or lactams, and satisfies the following (a) to (d).
(A) Underwater equilibrium water absorption ≦ 3.0% of the polyamide resin composition
(B) The DSC melting peak temperature located on the lowest temperature side resulting from the polyamide resin of the polyamide resin composition is 290 ° C. to 350 ° C.
(C) A flame retardant combination (B) comprising a flame retardant (B-1) comprising a metal salt of phosphinic acid, a metal salt or a double salt containing phosphorous acid component and aluminum as constituent components (B-2) ) And a nitrogen-containing cyclic compound having an amino group. (D) Mass ratio of (B-1) component and (B-2) component of the flame retardant combination [(B-1) / ( B-2)] is 2.5 to 15   The semiaromatic polyamide resin (A) contains 55 mol% or more of a structural unit obtained from an equimolar molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid, and an aminocarboxylic acid having 11 to 18 carbon atoms. Or the flame-retardant polyamide resin composition of Claim 1 formed by copolymerizing 1 type, or multiple types of lactam. The semi-aromatic polyamide resin (A) is obtained from (a) 55 to 75 mol% of a structural unit obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, and (b) 11-aminoundecanoic acid or undecane lactam. claim 1 or 2 flame-retardant polyamide resin composition according to, characterized in that the structural unit 45-25 mole% is a semi-aromatic polyamide resin as a constituent to be. The semi-aromatic polyamide resin (A) is (a ′) 82 to 98 mol% of a structural unit obtained from an equivalent molar salt of decamethylenediamine and terephthalic acid, and (b ′) 11-aminoundecanoic acid or undecane lactam. claim 1 or 2 flame-retardant polyamide resin composition according to characterized in that it is a semi-aromatic polyamide resin as a constituent unit 18-2 mol% constituents derived from. The molded body formed using the polyamide resin composition is characterized in that no bleed product is produced on the surface of the molded body even after 200 hours in an environment of 80 ° C and 85% RH. 5. The flame retardant polyamide resin composition according to any one of 4 above.