KR101932808B1

KR101932808B1 - Flame-retardant polyamide resin composition

Info

Publication number: KR101932808B1
Application number: KR1020157036949A
Authority: KR
Inventors: 마코토 다마츠시마; 쥰이치 나카오
Original assignee: 도요보 가부시키가이샤
Priority date: 2013-08-05
Filing date: 2014-07-28
Publication date: 2018-12-27
Also published as: WO2015019882A1; CN105377989A; KR20160039578A; JPWO2015019882A1; TWI615418B; JP5800096B2; CN105377989B; TW201509991A

Abstract

The flame-retardant polyamide resin composition of the present invention contains 30 parts by mass to 80 parts by mass of the flame retarder combination (B) and 40 parts by mass to 250 parts by mass of the reinforcing material (C) relative to 100 parts by mass of the semi-aromatic polyamide resin (A) A flame-retardant polyamide resin composition having a flame retardant polyamide resin composition having an underwater equilibrium absorption rate of 3.0% or less, a DSC melting peak temperature of 290 ° C to 350 ° C, a flame retardant combination (B) , High melting point, flame retardance, anti-bleed-out property and low absorbency.

Description

FLAME-RETARDANT POLYAMIDE RESIN COMPOSITION [0001]

The present invention relates to a molded article obtained by using a polyamide resin composition which is softened by a high melting point and also by a non-halogen flame retardant, and which does not bleed out under a use environment and exhibits stable mechanical properties, dimensional stability To a flame-retardant polyamide resin composition.

Of the thermoplastic resins, polyamide resins have been used for medical and industrial materials fibers and engineering plastics, taking advantage of their excellent properties and ease of melt molding. In particular, engineering plastics are not limited to automobile parts and industrial machine parts, but are used in various industrial fields such as various industrial parts, case parts, and electric and electronic parts.

2. Description of the Related Art Recently, with respect to electrical and electronic parts, surface mounting methods (flow methods, reflow methods) have been rapidly infiltrated due to miniaturization of parts, miniaturization of mounting parts, . In the surface mount method, the temperature of the process atmosphere is higher than the solder melting temperature (240 ° C to 260 ° C), so that the resin used necessarily requires heat resistance at the ambient temperature. Further, in the surface mounting step, the expansion and deformation of the mounting parts resulting from the absorption of the resin may become a problem, and the resin to be used is required to have low water absorption. As resins satisfying these properties, aromatic polyamides including 6T polyamide are used for surface-mounted electrical and electronic parts.

On the other hand, it is said that the polyamide resin to be the raw material preferably has flame retardancy based on the UL-94 standard, depending on the part or environment in which the molded article formed from the polyamide resin is used. According to this necessity, various techniques for imparting flame retardancy to the polyamide resin have been developed so far. As a technique for flame retarding a polyamide resin, a halogenated organic compound such as brominated polystyrene which is a flame retardant is generally used in combination with an antimony compound serving as a flame retarding aid. However, this technique is capable of imparting excellent flame retardancy, but also has a problem of generation of hydrogen halide during combustion and a large amount of fuming. In addition, the non-halogen flame-retardant polyamide resin has been actively studied for its continued use of plastic products using some halogen-based flame retardants.

As a non-halogen flame retarding technique, metal hydroxides or phosphorus compounds are generally used as flame retardants. However, in order to obtain sufficient flame retardancy, electrons are required to be added in a large amount, and as a result, there is a problem that the mechanical properties are remarkably deteriorated.

On the other hand, in the latter, for example, Patent Document 1 discloses a halogen-free flame-retardant polyamide resin having high flame retardancy imparted to polyamide 66 by using a phosphorus compound containing melamine, melamine and melem, which are triazine compounds, Compositions have been proposed. In addition, Patent Document 2 proposes a halogen-free flame retardant polyamide resin composition imparting flame retardancy to polyamide 46 by using a nitrogen-containing compound in combination with a phosphorus-based flame retardant. However, these flame retardant polyamide resin compositions have excellent flame retardant properties, but under the actual use environment, remarkable strength deterioration occurs due to the inherent absorbency of the polyamide resin, so that the anticipated characteristics can not be exhibited. When these flame retardant resin compositions are examined as surface-mounted electrical and electronic parts, polyamide 66 is insufficient in heat resistance and polyamide 46 satisfies heat resistance. However, when the product is transported or stored, Therefore, it poses problems such as the expansion (blister) of the product in the surface mounting process. In addition, the molded article formed from the flame-retardant polyamide resin composition exhibits a large amount of bleeding derived from the triazine-based compound contained in the resin composition on its surface under high-temperature and high-humidity environment, And does not satisfy the user's demand, and there is room for improvement.

Patent Document 3 proposes a flame retardant resin composition imparting 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. The patented technique seems to exert an excellent effect on almost all polyamides including high melting point polyamides. However, when a flame retardant containing a triazine type compound is applied to a high melting point polyamide represented by 6T type polyamide, Due to the lack of heat resistance or purity of the triazine compound, sublimation or thermal decomposition occurs, so that not only the appearance of the molded article is markedly lowered but also the generation of the bleed-out component originating from the triazine-based compound is accelerated, The problem that a large amount of bleed water is generated on the surface of the molded article formed of the resin composition can not be solved. In addition, the 6T type polyamide and the like have a high saturation absorption rate of 6%, and when they are applied to the surface mounting type electrical and electronic parts, the above-described blisters and the mechanical properties deteriorate remarkably due to absorption and dimensional changes occur. I have an assignment.

As described above, the halogen-based flame-retardant polyamide resins proposed so far do not satisfy all of the high melting point, the flame retardance, the bleed-out property, and the low water-absorbing property.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-43647 Patent Document 2: Japanese Patent No. 4454146 Patent Document 3: Japanese Patent No. 4951187

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and an object of the present invention is to provide a flame retardant polyamide resin composition for electrical and electronic devices which is excellent in flame retardance, bleeding resistance, high melting point and low water absorption.

The present inventors have found that, in order to achieve the above object, it is an object of the present invention to provide a flame retardant resin composition which is excellent in flame retardancy, hardly causes generation of bleeding water on the surface of a molded article under a room temperature environment such as high temperature and high humidity and has a high melting point, The composition of the reduced polyamide and the composition of the non-halogen flame retardant have been investigated. As a result, the present invention has been completed.

That is, the present invention has the following constitutions (1) to (4).

(1) A flame-retardant polyamide resin composition comprising 30 parts by mass to 80 parts by mass of a flame retarder combination (B) and 40 parts by mass to 250 parts by mass of a reinforcing material (C), based on 100 parts by mass of the semi-aromatic polyamide resin (A) A flame retardant polyamide resin composition characterized by satisfying the following (A) to (D):

(A) Equilibrium Water Absorption Rate of Polyamide Resin Composition?? 3.0%

(B) The DSC melting peak temperature at the lowest temperature side of the polyamide resin group of the polyamide resin composition is 290 to 350 DEG C

(B) a flame retardant agent (B-2) comprising a flame retardant (B-1) containing a metal salt of phosphinic acid and a metal salt or a salt containing a phosphorous acid component and aluminum as constituent , Does not include a nitrogen-containing cyclic compound having an amino group

(B-1) / (B-2)] of the components (B-1) and (B-

(2) the semiaromatic polyamide resin (A) contains at least 50 mol% of constitutional units obtained from an equimolar molar salt of a diamine having 2 to 12 carbon atoms with terephthalic acid, and further contains an aminocarboxylic acid having a carbon number of 11 to 18 The flame-retardant polyamide resin composition according to (1), wherein the flame-retardant polyamide resin composition is obtained by copolymerizing one or more species of lactam.

(3) The semi-aromatic polyamide resin (A) according to any one of (1) to (4), wherein the semiaromatic polyamide resin (A) contains 55 mol% or more of constitutional units obtained from an equimolar molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid, The flame-retardant polyamide resin composition according to (1), wherein the flame-retardant polyamide resin composition is obtained by copolymerizing one or more species of lactam.

(4), wherein the semiaromatic polyamide resin (A) comprises (a) from 55 mol% to 75 mol% of constitutional units obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, and (b) The flame-retardant polyamide resin composition according to any one of (1) to (3), wherein the flame-retardant polyamide resin composition is a semiaromatic polyamide resin comprising 45 mol% to 25 mol%

(5) The method according to any one of (1) to (5), wherein the semiaromatic polyamide resin (A) comprises (a ') from 82 mol% to 98 mol% of constitutional units obtained from an equivalent molar salt of decamethylene diamine and terephthalic acid, The flame-retardant polyamide resin composition according to any one of (1) to (3), wherein the flame-retardant polyamide resin composition is a semiaromatic polyamide resin comprising 18 mol% to 2 mol% of a constituent unit derived from a lactam.

(6) The molded article formed by using the polyamide resin composition described in any one of (1) to (5), wherein formation of bleeding is not observed on the surface of the molded article even after 200 hours elapse in an environment of 80 캜 and 85% RH Wherein the flame retardant polyamide resin composition is a flame retardant polyamide resin composition.

The flame retardant polyamide resin composition of the present invention has a high melting point and imparts excellent flame retardancy and mechanical strength by using a specific halogen-free flame retardant agent. In addition, Can be suppressed and the strength reduction or dimensional change due to the absorption of the polyamide resin can be reduced, and a product highly satisfying the user's demand can be manufactured.

The polyamide resin composition of the present invention is intended to be used in electric and electronic devices, electric and electronic parts mounted on automobiles, and cases of electric devices. More specifically, the polyamide resin composition of the present invention can be produced by injection molding all of these products, although a connector, a switch, a housing of an IC or an LED, a socket, a relay, a resistor, a capacitor, a coil bobbin, Can be manufactured.

The semiaromatic polyamide resin (A) used in the present invention is not particularly limited and is a semiaromatic polyamide having an acid amide bond (-CONH-) in the molecule and also having an aromatic ring (benzene ring).

Specific examples of the semi-aromatic polyamide include 6T polyamide (for example, polyamide 6T / 6I comprising terephthalic acid / isophthalic acid / hexamethylenediamine, polyamide 6T / 66 comprising terephthalic acid / adipic acid / hexamethylenediamine, terephthalic acid / Polyamide 6T / 6I / 66 composed of phthalic acid / adipic acid / hexamethylenediamine, polyamide 6T / 6I / 66 composed of terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine, terephthalic acid / hexamethylene Polyamide 6T / 6 composed of diamine /? -Caprolactam, polyamide 6T / 4T composed of terephthalic acid / hexamethylenediamine / tetramethylenediamine), 9T polyamide (terephthalic acid / 1,9-nonanediamine / (Terephthalic acid / 1,10-decanediamine), 12T-based polyamides (terephthalic acid / 1,12-dodecanediamine), sebacic acid / There may be mentioned a polyamide composed of a.

Since the polyamide resin composition of the present invention is required to correspond to the surface mounting technique which is a general manufacturing method in the use of electric and electronic parts, it is necessary that the melting point measured by the method described in the following examples is 290 to 350 캜 have. Here, the melting point refers to the melting peak temperature measured by DSC (differential scanning calorimeter) located on the lowest temperature side of the polyamide resin of the polyamide resin composition. The melting point is preferably 300 ° C to 340 ° C, more preferably 310 ° C to 340 ° C. When the melting point exceeds the upper limit, the processing temperature required for injection molding of the polyamide resin composition of the present invention becomes extremely high. Therefore, the possibility that the polyamide resin composition is thermally decomposed and the desired performance or appearance can not be obtained Which is undesirable. When the melting point is less than the above lower limit, heat resistance at the surface mounting step (230 ° C to 280 ° C) is insufficient, and there is a possibility that defects such as product deformation in the process may occur.

The polyamide resin composition of the present invention is required to cope with the surface mounting process. Further, due to the miniaturization and structural densification of electrical and electronic parts, the polyamide resin composition of the present invention can stably maintain strength and product dimensions even after the product is absorbed Is required. Therefore, it is necessary that the equilibrium water absorption rate measured by the method described in the following examples is 3.0% or less. Further, the water-to-water equilibrium absorption rate is preferably 2.5% or less. It is preferable that the lower limit of the water uptake equilibrium water absorption is 0%, but it is preferably about 1.5% in view of the characteristics of the semi-aromatic polyamide (A) used in the present invention. When the water absorption rate exceeds the upper limit, there is a possibility that a decrease in strength due to absorption and a dimensional change become remarkable, problems such as insufficient strength of the product, poor assembly, and the like may occur.

The semiaromatic polyamide resin (A) used in the present invention is preferably the following semiaromatic polyamide resin (A) from the viewpoints of the melting point and the equilibrium water absorption rate in water.

The semiaromatic polyamide resin (A) contains 50 mol% or more of constitutional units obtained from an equivalent molar salt of a diamine having 2 to 12 carbon atoms with terephthalic acid, and further contains an aminocarboxylic acid having 11 to 18 carbon atoms or one Or a semiaromatic polyamide resin obtained by copolymerizing a plurality of species. The constituent unit derived from the equivalent molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid is 50 mol% to 98 mol%, the aminocarboxylic acid having 11 to 18 carbon atoms or the lactam is composed of 2 mol% to 50 mol% Is more preferable.

As the diamine component having 2 to 12 carbon atoms constituting the semi-aromatic polyamide resin (A), an aliphatic diamine having 2 to 12 carbon atoms is preferable.

Examples of the diamine component having 2 to 12 carbon atoms constituting the semiaromatic polyamide resin (A) include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine Methyl-1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, , Octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine. These may be used singly or in combination.

In the case of a semiaromatic polyamide composed of a constitutional unit derived from an equivalent molar salt of a diamine having 9 or more carbon atoms and terephthalic acid, the melting point may be 290 DEG C or lower. A preferred embodiment is a polyamide resin having a constitutional unit of 50 mol% or more and a melting point on the lowermost side of 290 DEG C or more. If the amount of the constitutional unit derived from the equivalent molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid is less than 50 mol%, crystallinity and mechanical properties may be deteriorated.

In the case of a semiaromatic polyamide composed of a constitutional unit obtained from an equivalent molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid, by containing at least 55 mol% of the constitutional unit, a polyamide having a melting point on the lowermost side of 290 DEG C or higher It is also possible to use a resin, which is a preferred embodiment. 55 to 98% by mole of a constitutional unit obtained from an equivalent molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid, 2 to 45% by mole of one or more kinds of amicarboxylic acids or lactams having 11 to 18 carbon atoms, Is more preferable. When the amount of the constituent unit derived from the equivalent 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.

In the semiaromatic polyamide resin (A), other components may be copolymerized in an amount of 50 mol% or less of the constitutional units. Examples of the copolymerizable diamine component include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylene Aliphatic diamines such as diamine, alicyclic diamines such as piperazine, cyclohexane diamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'- aminocyclohexyl) Aromatic diamines such as xylylenediamine, p-xylylenediamine, paraphenylenediamine, and metaphenylenediamine, and hydrogenated products thereof.

Examples of the copolymerizable acid component include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-di Aromatic dicarboxylic acids such as phenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid and 5-hydroxyisophthalic acid, 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 Alicyclic or alicyclic dicarboxylic acids such as benzoic acid, 3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 4-methyl-1,2-cyclohexane dicarboxylic acid, And the like.

Examples of the copolymerizable component include lactam such as ε-caprolactam, 11-amino undecanoic acid, undecanolactam, 12-aminododecanoic acid and 12-lauryllactam, and aminocarboxylic acids such as a structure in which they are opened .

Among these components, as the copolymerization component, it is preferable that one or more kinds of aminocarboxylic acids having 11 to 18 carbon atoms or lactam having 11 to 18 carbon atoms are copolymerized.

When the copolymerization component is composed of a dicarboxylic acid and a diamine, depending on the combination, the melting point is less than 290 ° C, which is not preferable. The aminocarboxylic acid or lactam having a carbon number of 11 to 18 has a role of improving the moldability by adjusting the melting point and the temperature-rise crystallization temperature, the role of improving the trouble due to the change of physical properties and dimensional change at the time of absorption by reducing the absorption rate, And has a role of improving fluidity at the time of melting by introducing one skeleton.

The semiaromatic polyamide resin (A) used in the present invention is a copolymer comprising (a) 55 mol% to 75 mol% of constitutional units obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, (b) It is particularly preferable that the semiaromatic polyamide resin is constituted of 45 mol% to 25 mol% of constitutional units obtained from the lactam. At this time, the semiaromatic polyamide resin (A) may contain constituent units composed of the copolymerizable components other than the constituent units of (a) and the constituent units of (b) in a proportion of not more than 20 mol% good. By using the semiaromatic polyamide (A) comprising the constituent components, it is possible to realize excellent moldability in addition to high melting point, low absorption and high fluidity.

The semiaromatic polyamide resin (A) is blended in order to realize excellent moldability in addition to high heat resistance, fluidity and low water absorption, and is composed of a component (a) corresponding to 6T polyamide and a component Polyamide 6T / 6I composed of terephthalic acid / isophthalic acid / hexamethylene diamine, polyamide 6T / 66 composed of terephthalic acid / adipic acid / terephthalic acid) Polyamide 6T / 6I / 66 composed of terephthalic acid / isophthalic acid / adipic acid / hexamethylene diamine, polyamide 6T / M-5T composed of terephthalic acid / hexamethylene diamine / 2-methyl-1,5-pentamethylene diamine, And polyamide 6T / 6 composed of terephthalic acid / hexamethylenediamine / epsilon -caprolactam) is remarkably improved. In addition, since it has a flexible long-chain fatty skeleton derived from the 11 polyamide component, it also has a feature that fluidity can be secured easily.

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

The component (a) is a main component of the semiaromatic polyamide resin (A) and has a role of imparting excellent heat resistance, mechanical properties, and sliding properties to the semiaromatic polyamide resin (A). The mixing ratio of the component (a) in the semi-aromatic polyamide resin (A) is preferably from 55 mol% to 75 mol%, more preferably from 60 mol% to 70 mol%, still more preferably from 62 mol% 68 mol%. When the blending ratio of the component (a) is less than the lower limit described above, there is a possibility that the 6T polyamide as a crystal component is subjected to crystal inhibition by the copolymerization component, resulting in deterioration of moldability and high temperature characteristics. On the other hand, Is too high, there is a possibility of decomposition at the time of processing.

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

The component (b) is intended to improve water absorbability and fluidity, which is a drawback of the component (a), and serves to improve moldability by adjusting the melting point and temperature-rise crystallization temperature of the semiaromatic polyamide resin (A) And has a role of improving the trouble due to a change in physical properties and dimensional changes at the time of absorption and a function of improving the fluidity at the time of melting by introducing a flexible skeleton. The blending ratio of the component (b) in the semi-aromatic polyamide resin (A) is preferably from 45 mol% to 25 mol%, more preferably from 40 mol% to 30 mol%, still more preferably from 38 mol% 32 mol%. When the blending ratio of the component (b) is less than the lower limit described above, the melting point of the semi-aromatic polyamide (A) does not sufficiently lower and the moldability may be insufficient. There is a possibility that instability such as decrease in mechanical characteristics or change in dimensions is caused. When the upper limit is exceeded, the melting point of the semi-aromatic polyamide resin is excessively lowered and the crystallization speed is lowered, and the moldability tends to be deteriorated. On the other hand, the amount of the component (a) Or heat resistance may be insufficient.

The semiaromatic polyamide resin (A) used in the present invention is a copolymer of (a ') 82 mol% to 98 mol% of constitutional units obtained from an equimolar molar salt of decamethylene diamine and terephthalic acid, (b') 11- And is preferably a semiaromatic polyamide resin comprising constituent units derived from undecanoic acid or undecane lactam in an amount of 18 mol% to 2 mol%. At this time, the semiaromatic polyamide resin (A) contains constituent units composed of the copolymerizable components other than the constituent units (a ') and (b') in a proportion of not more than 15 mol% . By using the aromatic polyamide (A) comprising the present constituent component, it is possible to realize excellent moldability in addition to high melting point, low absorption and high fluidity.

The components (a ') and (b') are used for the same purpose as the component (b). The component (a ') uses a long-chain diamine than the component (a), and in order to balance the action of the component (b), the preferred mixing ratio of the component (a') is larger than that of the component .

Examples of the catalyst to be used in the production of the semi-aromatic polyamide resin (A) include phosphoric acid, phosphorous acid, hypophosphoric acid, metal salts thereof, ammonium salts and esters. 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 esters include ethyl esters, isopropyl esters, butyl esters, hexyl esters, isodecyl esters, octadecyl esters, decyl esters, stearyl esters and phenyl esters. From the viewpoint of improving the stability of melt retention, it is preferable to add an alkali compound such as sodium hydroxide, potassium hydroxide or magnesium hydroxide.

The relative viscosity (RV) measured in 96% concentrated sulfuric acid of the semi-aromatic polyamide resin (A) at 20 캜 is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and still more preferably 1.5 to 2.5. As a method of setting the relative viscosity of the polyamide within a certain range, a means for adjusting the molecular weight may be mentioned.

The terminal group and the molecular weight of the polyamide can be adjusted by a method of polycondensation by adjusting the molar ratio of the amount of amino groups to the amount of carboxyl groups, or a method of adding a terminal sealing agent to the semi-aromatic polyamide resin (A). When the molar ratio of the amino group and the carboxyl group is polycondensed at a certain ratio, the molar ratio (diamine / dicarboxylic acid) of the total diamine to the total dicarboxylic acid to be used is adjusted within the range of 1.00 / 1.05 to 1.10 / 1.00 desirable.

The time of adding the end sealant may be at the time of injecting the raw material, at the beginning of the polymerization, at the end of the polymerization, or at the end of the polymerization. The terminal sealing agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the terminal of the polyamide. An acid anhydride such as a monocarboxylic acid or a monoamine or phthalic anhydride, a monoisocyanate, Monoesters, monoalcohols, and the like. Examples of the terminal sealing agent include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, capronic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, Alicyclic monocarboxylic acids such as benzoic acid, cyclohexanecarboxylic acid, and the like; aromatic monocarboxylic acids such as benzoic acid, toluenic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, Examples of the acid anhydride include acid anhydrides such as acid, maleic anhydride, phthalic anhydride and hexahydrophthalic anhydride, and acid anhydrides such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, Aliphatic monoamines such as dipropylamine and dibutylamine, alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, And the like.

The acid value and the amine value of the semi-aromatic polyamide resin (A) are preferably 0 eq / ton to 200 eq / ton and 0 eq / ton to 100 eq / ton, respectively. When the terminal functional group is more than 200 eq / ton, gelation or deterioration is promoted at the time of melt retention, and problems such as coloration and hydrolysis are caused even under the use environment. On the other hand, when a reactive compound such as glass fiber or maleic acid modified polyolefin is compounded, the acid value and / or amine value is preferably 5 eq / ton to 100 eq / ton depending on the reactivity and the reactor.

The semiaromatic polyamide resin (A) can be produced by a conventionally known method. For example, the semiaromatic polyamide resin (A) can be easily synthesized by co-condensation reaction of raw material monomers. The order of the co-polymerization is not particularly limited, and all raw material monomers may be reacted at once, and some raw material monomers may be reacted first, followed by reacting the remaining raw material monomers. The polymerization method is not particularly limited, but it may be carried out in a continuous process from the injection of the raw material to the production of the polymer. Alternatively, the oligomer may be produced once and then the polymerization may be carried out by an extruder or the like in a separate step, Or the like may be used. By adjusting the injection ratio of the raw material monomer, the proportion of each constituent unit in the copolymerized polyamide to be synthesized can be controlled.

The semiaromatic polyamide resin (A) is preferably present in a proportion of 20% by mass to 70% by mass, more preferably 25% by mass to 55% by mass in the polyamide resin composition of the present invention do. If the ratio of the semi-aromatic polyamide resin (A) is less than the lower limit described above, the mechanical strength is lowered. If the ratio exceeds the upper limit, the blending amount of the flame retardant [(B-1) and (B- And it becomes difficult to obtain a desired effect.

The flame retardant (B-1) is blended for imparting flame retardancy to a molded article formed by the polyamide resin of the present invention, and examples thereof include phosphinates and / or diphosphates and / or polymers thereof. Specific examples include aluminum salts, calcium salts and zinc salts of methylethylphosphinic acid, aluminum salts of diethylphosphinic acid, calcium salts and zinc salts, and aluminum salts, calcium salts and zinc salts of methylpropylphosphinic acid. have. Particularly, from the viewpoint of stability, aluminum salts are preferable.

The flame retardant (B-2) is a mixture of a phosphorous acid component and an alkaline earth metal (Mg, Ca, Sr, Ba), a transition metal (Ti, Mn, Fe, Ni, Cu, Zr, Zn, Mo, Pb, (B-1), so as to exhibit a high level of flame retardancy. In particular, a metal salt mainly composed of aluminum hypophosphite is preferable from the viewpoint of stability and effects of the present invention. Aluminum phosphite may be foamable. Examples of the phosphorous acid metal salt or double salt include, for example, but not limited thereto.

The ratio of the total amount of the flame retardant [(B-1) and (B-2)] is 30 parts by mass to 80 parts by mass with respect to 100 parts by mass of the polyamide resin (A). The amount is preferably from 35 parts by mass to 75 parts by mass, and more preferably from 40 parts by mass to 70 parts by mass. If the total amount of the flame retardant [(B-1) and (B-2)] is less than the lower limit described above, the desired high flame retardancy can not be obtained. If the total content exceeds the upper limit, Which is not preferable.

In particular, in the case of using the above-described semi-aromatic polyamide resin (A) selected from the viewpoints of the melting point and the water absorption rate in water, the amount of the above-mentioned compounding is important in order to obtain high flame retardancy.

The blend mass ratio [(B-1) / (B-2)] of the flame retardant [(B-1) and (B-2)] is important for coexistence of high flame retardancy and mechanical properties, ) / (B-2)] is required to be in the range of 2.5 to 15. [(B-1) / (B-2)] is preferably 2.8 to 13, more preferably 3.0 to 11. If the blend mass ratio [(B-1) / (B-2)] of the flame retardant deviates from the above range, the desired high flame retardancy may not be obtained.

The combination of the flame retardant [(B-1), (B-2)] is important for obtaining the resin composition having the high melting point, low absorption, high flame retardancy and bleed out property. Particularly, it is possible to exhibit a high flame retardancy without using a nitrogen-containing cyclic compound having an amino group, which has been conventionally used for obtaining a high flame retardancy, and further, in an actual use environment such as high temperature and humidity, It is possible to provide a product which can be stably used without being influenced by the use environment. The flame-retardant polyamide resin composition of the present invention has a high flame retardancy even when a specific nitrogen-containing cyclic compound having an amino group, which is widely used as a flame retardant, is not used in the case of using the above-mentioned semi-aromatic polyamide resin (A) And the suppression of the bleed product on the surface of the product under practical use environments such as humidity and humidity can be achieved.

The reinforcing material (C) is blended to improve the moldability of the polyamide resin composition and the strength of the molded article, and it is preferable to use at least one selected from the fibrous reinforcement material and the needle-shaped reinforcement material. Examples of the acicular reinforcing material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, calcium carbonate whisker, magnesium sulfate whisker, calcium carbonate whisker, , And wollastonite. As the glass fiber, it is possible to use cut glass fiber or continuous filament fiber having a length of 0.1 mm to 100 mm. As the cross-sectional shape of the glass fiber, glass fibers 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 占 퐉 or less, preferably 15 占 퐉 or less, more preferably 10 占 퐉 or less. In addition, glass fibers having a non-circular cross section are preferable from the viewpoint of physical properties and fluidity. The glass fiber having a non-circular cross-section includes those having a substantially elliptical shape, a substantially circular shape, and a roughly oblong shape in cross section perpendicular to the longitudinal direction of the fiber length, and the flatness is preferably 1.5 to 8. Here, the flatness means a rectangular area having a minimum area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, assuming that the length of the long side of the rectangle is the long diameter, and the length of the short side is the end diameter. / Is the ratio of the diameter to the diameter. The thickness of the glass fiber is not particularly limited, but its diameter is 1 mu m to 20 mu m and its long diameter is about 2 mu m to 100 mu m. In addition, the glass fiber is preferably a cut glass fiber type fiber cut into a fiber and having a fiber length of about 1 mm to 20 mm. In order to improve the affinity with the polyamide resin, the fibrous reinforcement is preferably treated with an organic treatment or a coupling agent or in combination with a coupling agent at the time of the melting compound. Examples of the coupling agent include silane coupling agents, A titanate-based coupling agent, and an aluminum-based coupling agent may be used. Among them, an aminosilane coupling agent and an epoxy silane coupling agent are particularly preferable.

The ratio of the reinforcing material (C) is required to sufficiently exhibit the mechanical properties of 40 parts by mass to 250 parts by mass with respect to 100 parts by mass of the polyamide resin (A). The amount is preferably 50 parts by mass to 220 parts by mass, and more preferably 60 parts by mass to 200 parts by mass. If the ratio of the reinforcing material (C) is less than the above lower limit, the mechanical strength of the molded article is lowered, and if it exceeds the upper limit, the extrudability and molding processability may deteriorate.

In the polyamide resin composition of the present invention, various additives of conventional polyamide resin compositions for electric and electronic components can be used. Examples of the additives include thermoplastic resins other than polyamides and polyamides which are different from stabilizers, impact modifiers, mold release agents, sliding property modifiers, colorants, plasticizers, nucleating agents, and semiaromatic polyamide resins (A). The total amount of these components in the polyamide resin composition is preferably 30 mass% or less, more preferably 20 mass% or less, and more preferably 10 mass% Or less, more preferably 5 mass% or less.

Examples of the stabilizer include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants and phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones and imidazoles, ultraviolet absorbers, metal deactivators, Copper compounds and the like. Examples of the copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, cupric sulfate, copper nitrate , Copper salts of organic carboxylic acids such as copper acetate, and the like. Examples of the halogenated alkali metal compounds include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride , Potassium bromide, potassium iodide and the like. These additives may be used not only singly but also in combination of several kinds. The amount of the stabilizer to be added may be selected in an optimum amount, but it is possible to add up to 5 parts by mass 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 semiaromatic polyamide resin (A). The polyamide having a composition different from that of the semiaromatic polyamide resin (A) of the present invention is not particularly limited, but examples thereof include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polymethoxy silylene adipamide (polyamide MXD6), polyparaxylylene adipamide Polyamide PXD6), polytetramethylene cevacamide (polyamide 410), polyhexamethylene cevacamide (polyamide 610), polydecamethylene adipamide (polyamide 106), poly decamethylene cevacamide (polyamide (Polyamide 610), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 611), polyhexamethylene terephthalamide (polyamide 610), polyhexamethylene terephthalamide , Polytetramethylene terephthalamide (polyamide 4T), polypentamethylene terephthalamide (polyamide 5T), poly-2-methylpentamethylene terephthalamide (polyamide M-5T), polyhexamethylenehexahydroterephthalamide 6T (H)), poly 2-methyl-octamethylene terephthalamide, polynonamethylene terephthalamide (polyamide 9T), polydecamethylene terephthalamide (polyamide 10T), polyundecamethylene terephthalamide (polyamide 11T) (3-methyl-4-aminohexyl) methane terephthalamide (polyamide PACMT), polybis (3-methyl-4-aminohexyl) methaneisophthalamide (Polyamide PACMI), polybis (3-methyl-4-aminohexyl) methanedodecamide (polyamide PACM12), polybis Polyalkyl ether copolymer Polyamides, or polyamides thereof may be used alone or in combination of two or more. Of these, polyamide 66 or polyamide 6T / 66 or the like may be blended with a polyamide 10T derivative or the like for imparting additional low water absorption properties in order to improve the crystallization speed and the moldability. The amount of the polyamide having a different composition from that of the semi-aromatic polyamide resin (A) may be selected in an optimum amount, but it is possible to add up to 50 parts by mass to 100 parts by mass of the semi-aromatic polyamide resin (A).

A thermoplastic resin other than polyamide having a composition different from that of the semiaromatic polyamide resin (A) may be added to the polyamide resin composition of the present invention. Examples of the polymer other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide (PAI), polyetherketone ketone (PEKK), polyphenylene ether (PPE), polyethersulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutyl (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene (PS), poly (ethylene terephthalate), polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate Styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), and acrylonitrile-butadiene-styrene copolymer (ABS). These thermoplastic resins may be blended in a molten state by melt kneading, but thermoplastic resins may be dispersed in the polyamide resin composition of the present invention in the form of fibers or particles. The amount of the thermoplastic resin to be added may be selected in an optimum amount, but it is possible to add up to 50 parts by mass to 100 parts by mass of the semi-aromatic polyamide resin (A).

Examples of the impact modifier include an ethylene-propylene rubber (EPM), an ethylene-propylene-diene rubber (EPDM), an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, an ethylene-methacrylic acid copolymer, Styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS) , Acrylic acid ester copolymer, polybutylene terephthalate or polybutylene naphthalate as a hard segment and polytetramethylene glycol or polycaprolactone or polycarbonate diol as a soft segment, , Polyamide elastomer, urethane elastomer, acrylic elastomer, silicone rubber, fire System may be a rubber, such as polymer particles having a core shell structure consisting of polymers of different kinds. The amount of the impact modifier to be added may be selected in an optimum amount, but it is possible to add up to 30 parts by mass to 100 parts by mass of the semi-aromatic polyamide resin (A).

When a thermoplastic resin and an impact modifier other than the semiaromatic polyamide resin (A) are added to the polyamide resin composition of the present invention, a reactive group capable of reacting with the polyamide is preferably copolymerized. As the reactive group, poly A carboxyl group and a main chain amide group which are terminal groups of the amide resin. Specific examples thereof include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, and an isocyanate group. Of these, an acid anhydride group is most excellent in reactivity. It has been reported that the thermoplastic resin having a reactive group reactive with the polyamide resin is finely dispersed in the polyamide and thus the distance between the particles is shortened to greatly improve the impact resistance [S, Wu: Polymer 26 , 1855 (1985)).

Examples of the release agent include long-chain fatty acids or esters or metal salts thereof, amide compounds, polyethylene waxes, silicones, and polyethylene oxides. Examples of the long-chain fatty acid are preferably 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid and the like. Even if the partial or total carboxylic acid is esterified with monoglycol or polyglycol Or a metal salt may be formed. Examples of the amide compound include ethylenebisterephthalamide and methylenebisstearylamide. These release agents may be used alone or as a mixture. The amount of the releasing agent to be added may be an optimum amount, but it is possible to add up to 5 parts by mass to 100 parts by mass of the semi-aromatic polyamide resin (A).

The flame retardant polyamide resin composition of the present invention is capable of imparting excellent flame retardancy by optimizing the combination of flame retardant agents and is capable of imparting a high level of bleed water production on the surface of a molded article under a practical use environment, Lt; / RTI > By using the semi-aromatic polyamide resin (A) having a melting point of 290 ° C to 350 ° C and an equilibrium water absorption rate of 3.0% or less, it has a high melting point, It is possible to obtain a flame-retardant polyamide resin composition having excellent properties such as suppressing the change and to provide a product highly satisfying the user's demand.

The polyamide resin composition of the present invention can be produced by blending each of the above-mentioned respective components by a conventionally known method. For example, it is possible to add each component in the polycondensation reaction of the semi-aromatic polyamide resin (A), dry-blend the semiaromatic polyamide resin (A) and other components, or use a twin-screw extruder And a method of melting and kneading each constituent component.

The polyamide resin composition of the present invention can be molded by conventionally known methods such as extrusion molding, injection molding, compression molding and the like. The molded product thus formed is excellent in flame retardancy and processability and can be used for various purposes. Specifically, various electrical and electronic parts such as connectors and switches, case parts, and the like can be cited, but the present invention is not limited thereto.

The molded article formed using the polyamide resin composition of the present invention is characterized in that no bleeding is formed on the surface of the molded article even after 200 hours elapse in an environment of 80 캜 and 85% RH.

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. The measurement values described in the examples were measured by the following methods.

(1) Relative viscosity

0.25 g of a polyamide resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 占 폚 using an Oswald viscometer.

(2) Melting point (Tm)

A test piece for UL combustion test having a length of 127 mm, a width of 12.6 mm and a thickness of 0.8 mm was set at a cylinder temperature of 20 DEG C and a mold temperature of 35 DEG C using a Toshiba KIKAI Injection Molding Machine EC-100 And injection molding was carried out to prepare a test piece. In order to measure the melting point (Tm) of the obtained molded article, a part of the molded article was weighed in an aluminum pan in an amount of 5 mg and sealed with an aluminum cover to prepare a measurement sample, and then a differential scanning calorimeter (manufactured by SEIKO INSTRUMENTS, SSC / 5200 ), The temperature was raised from room temperature to 20 DEG C / min in a nitrogen atmosphere, and the measurement was performed up to the melting point + 30 DEG C of the resin. At that time, the peak top temperature observed on the lowermost side among the peaks of the endotherm due to melting obtained was defined as the melting point (Tm).

(3) Water absorption rate

A flat plate having a length of 100 mm, a width of 100 mm and a thickness of 1 mm was injection-molded by setting the cylinder temperature at a temperature of the resin + 20 占 폚 and the mold temperature at 135 占 폚, . The test piece was annealed in an atmosphere of 140 ° C for 2 hours, and then the weight thereof was measured. Further, the annealed specimen was immersed in hot water at 80 캜 for 50 hours, and the weight thereof was measured, and the weight at that time was regarded as the weight at the time of saturated absorption. The equilibrium water uptake rate in water was determined from the following equations from the saturation absorption and the weight during drying measured by the above-mentioned method.

Water absorption rate (%) = {(weight at saturation absorption - weight at drying) / weight at drying} x 100

(4) Bending strength retention

Toshiba Kikai injection molding machine EC-100 was used. The cylinder temperature was set to the melting point of the resin + 20 占 폚, the mold temperature was set at 135 占 폚, and test pieces for evaluation were prepared in accordance with ISO 294-1. The prepared test pieces were annealed in an atmosphere at 140 캜 for 2 hours, and then some of them were subjected to evaluation of bending properties according to ISO 178. Further, the remaining test pieces after the annealing treatment were allowed to stand in an atmosphere at 85 캜 and 85% RH (relative humidity) for 1000 hours, and then evaluated for bending properties according to ISO 178. The bending strength retention after absorption was obtained from the bending strength after annealing and after the saturated absorption by the following equation.

(%) = (Bending strength after saturation absorption / bending strength after annealing) x 100

(5) Bending strength at the time of drying

Toshiba Kikai injection molding machine EC-100 was used. The cylinder temperature was set to the melting point of the resin + 20 占 폚, the mold temperature was set at 135 占 폚, and test pieces for evaluation were prepared in accordance with ISO 294-1. The produced test pieces were evaluated for bending properties according to ISO 178. The bending strength was determined based on the following criteria.

&Amp; cir &: Bending strength during drying > = 170 MPa

X: Bending strength in dry < 170 MPa

(6) Flammability

The injection molding machine EC-100 manufactured by Toshiba KIKAI Co., Ltd. was used. The cylinder temperature was set at a melting point of the resin + 20 DEG C and the mold temperature was set at 135 DEG C, and a test piece for evaluation having a length of 127 mm, a width of 12.7 mm and a thickness of 1.6 mm was injection- Respectively. Using this test piece, evaluation of flame retardancy was carried out in accordance with UL-94 vertical burning test.

(7) My bleed out castle

A flat plate having a length of 100 mm, a width of 100 mm and a thickness of 1 mm was injection-molded by setting the cylinder temperature to the melting point of the resin + 20 占 폚 and the mold temperature to 135 占 폚, . The test piece for evaluation was allowed to stand in an atmosphere of 80 ° C and 85% RH (relative humidity) for 200 hours, and the generation status of the bleed on the surface of the test piece was visually observed and confirmed on the basis of the following criteria.

○: No generation of bleed water

X: With bleed water generation

This example is carried out using the semi-aromatic polyamide resin (A) synthesized as illustrated below.

&Lt; 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 modifier and 17.52 kg of ion-exchanged water were injected into a 50 liter autoclave Then, N ₂ was pressurized from normal pressure to 0.05 MPa, and the pressure was returned to normal pressure. This operation was repeated three times, followed by N ₂ substitution, and then uniformly dissolved under stirring at 135 ° C and 0.3 MPa. Thereafter, the solution was continuously fed by a feed pump, heated to 240 캜 by a heating pipe, and heated for 1 hour. Thereafter, a reaction mixture was supplied to the pressurized reaction tube, heated to 290 DEG C, and part of the water was flowed out so as to keep the internal pressure at 3 MPa to obtain a lower condensate. Thereafter, the lower condensate was directly fed to a twin-screw extruder (screw diameter 37 mm, L / D = 60) while maintaining the molten state, and water was withdrawn from the vents at three points at a resin temperature of 335 DEG C, , To thereby 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. Table 1 shows the constituent monomer ratios of the semiaromatic polyamide resin (A) of Synthesis Example 1.

&Lt; 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, adipic acid (dicarboxylic acid other than terephthalic acid Acid), and the resin temperature of the twin-screw extruder was changed to 330 캜. A semiaromatic polyamide resin (A) was synthesized in the same manner as in Synthesis Example 1 except for these. The obtained semi-aromatic polyamide resin (A) had a relative viscosity of 2.1 and a melting point of 310 캜. Table 1 shows the constituent monomer ratios of the semiaromatic polyamide resin (A) of Synthesis Example 2.

&Lt; Synthesis Example 3 &

7.04 kg of 11-amino undecanoic acid was changed to undecanactam 6.41 kg, and the resin temperature of the twin-screw extruder was changed to 335 ° C. A semiaromatic polyamide resin (A) was synthesized in the same manner as in Synthesis Example 1 except for these. 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 semiaromatic polyamide resin (A) of Synthesis Example 3.

&Lt; Synthesis Example 4 &

15.51 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 modifier and 17.52 kg of ion-exchanged water were injected into a 50 liter autoclave , And a semiaromatic polyamide resin (A) was synthesized in the same manner as in Synthesis Example 1. The obtained semi-aromatic polyamide resin (A) had 10 T / 11 = 90/10 (molar ratio), a relative viscosity of 2.0, and a melting point of 304 占 폚.

&Lt; Synthesis Example 5 &

(Terephthalic acid unit: adipic acid unit molar ratio of 63:37) of terephthalic acid unit and adipic acid unit, and 1,6-hexamethylene diamine unit (molar ratio of terephthalic acid unit: adipic acid unit) of the terephthalic acid unit and the adipic acid unit were changed according to the method described in the Example 1 of the publication No. WO06 / 112300 Were synthesized in the same manner as in Example 1, The obtained semi-aromatic polyamide resin (A) had a relative viscosity of 2.1 and a melting point of 320 캜. Table 1 shows the constituent monomer ratios of the comparative semi-aromatic polyamide resin (A).

Examples 1 to 6 and Comparative Examples 1 to 11

Kneaded at the melting point of each polyamide raw material + 20 占 폚 using a twin-screw extruder STS-35 manufactured by Copper Co., Ltd. in the mass ratio (parts by mass) to the components described in Tables 2 and 3, The polyamide resin compositions of Comparative Examples 1 to 11 were obtained. The raw materials used in the production 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 materials: The semiaromatic polyamide resin (A), PA6T / 6 (polyamide 6T / 6) (Ultramide TM KR4351 manufactured by BASF) manufactured according to Synthesis Examples 1 to 5,

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 Taiheikagaku)

Flame retardant: melamine polyphosphate (MELAPUR (registered trademark) 200/70, manufactured by BASF)

Reinforcing material (C): glass fiber (T-275H, manufactured by Nihon Denkimarasu Co., Ltd.)

Release agent: Magnesium stearate

Stabilizer: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox1010 manufactured by Chiba Specialty Chemicals)

As is apparent from Table 2, in Examples 1 to 6, not only the flame retardancy (flame retardancy is V-0) but also the bending strength during drying is a sufficient value (170 MPa or more) to maintain the strength as a product, The bending strength retention ratio at the time of use is very high and stable characteristics are exhibited even in a high temperature and high humidity environment and satisfactory bleeding-out resistance is exhibited. On the other hand, as is clear from Table 3, in Comparative Examples 1 to 3, the balance of the flame retardant [(B-1) and (B-2)] is not optimal and sufficient flame retardancy can not be exhibited. In Comparative Example 4, the flame retardancy, the low water absorption, the bending strength retention at the time of absorption, and the bleeding-out property were satisfied, but the bending strength at the time of drying was remarkably lowered due to the excess amount of the flame retardant, . In Comparative Examples 5 and 6, flame retardancy and bleed-out resistance are satisfied, but the bending strength retention ratio upon absorption is low, and the characteristics can not be stably exhibited according to the use environment conditions, which may lead to defective products. In Comparative Example 7, the flame retardant combination of Examples contained melamine polyphosphate, which satisfied flame retardancy, bending strength at the time of drying, bending strength retention at the time of absorption, and the like. However, since the bleeding out property was poor, There is a possibility of causing. In Comparative Example 8, stable flame retardancy can be exhibited similarly to the embodiment by changing the combination of the flame retardant agent and the flame retardant agent (B-1) to a combination of melamine polyphosphate. However, There is a possibility of causing. Comparative Examples 9 and 10 can exhibit stable flame retardancy similarly to Comparative Example 8, but have a low bending strength retention at the time of absorption and have a low bleeding-out property. Therefore, cracks and appearance defects There is a possibility of doing. In Comparative Example 11, only the flame retardant (B-1) was blended, and sufficient flame retardancy could not be exhibited.

INDUSTRIAL APPLICABILITY The flame retardant polyamide resin composition of the present invention can exhibit excellent flame retardancy and strength by using a specific combination of a specific halogen-free flame retardant composition in an optimum amount, It is possible to inhibit the formation of water and to reduce the strength reduction and the dimensional change due to the absorption of the polyamide resin and to industrially advantageously produce a molded article highly satisfying the user's demand.

Claims

A flame-retardant polyamide resin composition comprising 30 parts by mass to 80 parts by mass of a flame retardant combination (B) and 40 parts by mass to 250 parts by mass of a reinforcing material (C) based on 100 parts by mass of the semi-aromatic polyamide resin (A) Wherein the polyamide resin (A) contains at least 50 mol% of a constitutional unit obtained from an equivalent molar salt of a diamine having 2 to 12 carbon atoms with terephthalic acid, and at least one aminocarboxylic acid or lactam having a carbon number of 11 to 18 Aromatic polyamide resin obtained by copolymerizing two or more aromatic polyamide resins,
A flame retardant polyamide resin composition characterized by satisfying the following (A) to (D):
(A) Equilibrium Water Absorption Rate of Polyamide Resin Composition?? 3.0%
(B) The DSC melting peak temperature at the lowest temperature side of the polyamide resin of the polyamide resin composition is 290 to 350 DEG C
(B) a flame retardant agent (B-2) comprising a flame retardant (B-1) containing a metal salt of phosphinic acid and a metal salt or a salt containing a phosphorous acid component and aluminum as constituent , Does not include a nitrogen-containing cyclic compound having an amino group
(B-1) / (B-2)] of the components (B-1) and (B-

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The polyimide resin composition according to claim 1, wherein the semiaromatic polyamide resin (A) contains at least 55 mol% of a constitutional unit obtained from an equimolar molar salt of a diamine having 6 to 10 carbon atoms with terephthalic acid, Wherein the flame retardant polyamide resin composition is obtained by copolymerizing one or more kinds of unsaturated carboxylic acids or a lactam.

The antireflection film as claimed in claim 1 or 3, wherein the semiaromatic polyamide resin (A) comprises (a) from 55 mol% to 75 mol% of constitutional units obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, (b) Aromatic polyamide resin composition comprising 45 mol% to 25 mol% of constitutional units obtained from aminoundecanoic acid or undecanactam as a constituent component.

The antireflection film as claimed in claim 1 or 3, wherein the semiaromatic polyamide resin (A) comprises (a ') from 82 mol% to 98 mol% of constitutional units obtained from the equivalent molar salt of decamethylene diamine and terephthalic acid, Aromatic polyamide resin composition comprising 18 mol% to 2 mol% of constituent units derived from 11-amino undecanoic acid or undecane lactam as a constituent component.

4. The molded article formed by using the polyamide resin composition according to any one of claims 1 to 3, characterized in that no generation of bleeding is observed on the surface of the molded article even after 200 hours elapse in an environment of 80 캜 and 85% RH. Amide resin composition.

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