JP2003128913A - Flame-retardant polyamide resin composition and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polyamide resin composition having excellent heat-resistance, low hygroscopicity, flame-retardance and tracking resistance and, accordingly, suitable especially as a molding material for electric parts and electronic parts. SOLUTION: The flame-retardant polyamide resin composition contains (A) a polyamide resin, (B) a bromine-containing flame-retardant, (C) a zinc- containing compound oxide and (D) an antimony-containing compound. In the repeating units constituting the polyamide resin A, the repeating unit derived from diamine is a unit derived from a 6-12C aliphatic diamine and the repeating unit derived from dicarboxylic acid is composed of 40-100 mol% repeating unit derived from terephthalic acid and 0-60 mol% repeating units derived from the other dicarboxylic acids based on the total molar number of the repeating units derived from all dicarboxylic acids.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamide resin,
The present invention relates to a polyamide resin composition and a molded product thereof. More specifically, the present invention is suitable for molded article materials for use in electrical parts and electronic parts, in particular, heat resistance, low water absorption, flame retardancy,
The present invention also relates to a polyamide resin composition having excellent tracking resistance, and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, as a polyamide, 6 nylon,
66 nylon and the like are widely known. Since these aliphatic polyamides have excellent moldability,
Widely used in electrical / electronic parts and mechanical parts.
Generally, development of high heat resistant polyamide resin is active, and
High heat-resistant resin compositions containing nylon and the like have been put into practical use, but they cannot be said to have sufficient heat distortion temperature. On the other hand, nylon 46 is known as a high heat-resistant polyamide, but its heat distortion resistance temperature is higher than that of conventional polyamides, but it has a problem of high water absorption.

Under the above circumstances, the applicant of the present invention has filed patent 29
No. 04859, (a) the dicarboxylic acid component unit is composed of 52 to 58 mol% of a terephthalic acid component unit and 48 to 42 mol% of an aliphatic dicarboxylic acid component unit,
(B) The diamine component unit is composed of an aliphatic alkylenediamine component unit and / or an alicyclic alkylenediamine component unit, and has an intrinsic viscosity [η] of 0.5 to 3.0 dl measured at 25 ° C. in concentrated sulfuric acid. It proposes a polyamide resin composition containing an aromatic polyamide in the range of / g and a fibrous filler. Since the polyamide resin composition is relatively excellent in heat resistance, water resistance, mechanical strength, impact resistance, etc., it is widely used as a molding material for automobile parts, electric / electronic parts and the like.

By the way, electric parts such as a current breaker and a contactor which require durability against a high voltage are electric devices which are used without the attention of a person, and are parts to which a load is continuously applied. Therefore, it is necessary to give sufficient consideration to safety.

[0005] Examples of such safety standards include the following. Ie UL
The flame retardancy is V-0 in the vertical combustion test according to 94, and the comparative tracking index (CT) in the test regarding the comparative tracking index according to UL 746A.
I) is 600 V or higher, that is, the operating level range (PL
C) is required to be 0.

Although studies on polyamide compositions satisfying such conditions have been made so far, it is not always the case that polyamide compositions having sufficient heat resistance and satisfying the above conditions have been provided. There wasn't. For example, JP-A-5-9379 and JP-A-11-1721.
No. 01 proposes a polyamide resin composition having a flame retardancy of V-0 according to the above-mentioned flame retardancy test.
Is less than 600V, that is, PLC
Was 1 or 2.

Further, International Publication WO98 / 14510
In No. 1, a flame-retardant polyamide resin comprising sodium antimonate, zinc borate, and a bromine-based flame retardant, which is excellent in coloring stability, achieves V—O in the flame retardancy test, and retains stability. Although it has been described that it has excellent properties, the result of a test conducted by the present inventor is that the use thereof may be limited when it is used for a high voltage component because of its low CTI value.

[0008]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and particularly, heat resistance, which is suitable as a molding material for use in electric parts and electronic parts, An object of the present invention is to provide a polyamide resin composition excellent in low water absorption, flame retardancy and tracking resistance, and a molded article thereof.

[0009]

Means for Solving the Problems In order to overcome the above-mentioned problems, the present inventors have made further detailed investigations on the components constituting the flame-retardant polyamide resin composition, and as a result, particularly electric parts and electronic parts. The invention has been completed for the flame-retardant polyamide resin composition according to the present application, which is suitable as a molding material for the above-mentioned application and is excellent in heat resistance, low water absorption, flame retardancy and tracking resistance. The present invention includes the following [1] to [1]
[0]].

[1] A polyamide resin as the component (A), a bromine-containing flame retardant as the component (B), a zinc-containing composite oxide as the component (C), and an antimony-containing compound as the component (D). In the flame-retardant polyamide resin composition, the repeating unit constituting the molecule of the polyamide resin of the component (A) is a repeating unit derived from a diamine, which is a repeating unit derived from an aliphatic diamine having 6 to 12 carbon atoms. The dicarboxylic acid-derived repeating unit has a terephthalic acid-derived repeating unit content of 40 to 100 based on the total number of moles of all dicarboxylic acid-derived repeating units.
0% to 60% by mole of repeating units derived from aromatic dicarboxylic acids other than terephthalic acid and / or repeating units derived from aliphatic dicarboxylic acids having 4 to 20 carbon atoms
A flame-retardant polyamide resin composition, characterized in that

[2] In addition to a polyamide resin as the component (A), a bromine-containing flame retardant as the component (B), a zinc-containing composite oxide as the component (C), and an antimony-containing compound as the component (D), Furthermore, a flame-retardant polyamide resin composition comprising a fibrous filler as the component (E) and / or an aliphatic polyamide as the component (F), which comprises the polyamide resin of the component (A). Regarding the repeating unit constituting the molecule, the diamine-derived repeating unit is an aliphatic diamine-derived repeating unit having 6 to 12 carbon atoms, and the dicarboxylic acid-derived repeating unit is based on the total number of moles of all dicarboxylic acid-derived repeating units, The repeating unit derived from terephthalic acid is 40 to 100 mol%,
A flame-retardant polyamide, characterized in that the repeating unit derived from an aromatic dicarboxylic acid other than terephthalic acid and / or the repeating unit derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms is 0 to 60 mol%. Resin composition.

[3] The composition ratio of the components (A) to (D) is based on the total weight of the components (A) to (D).
The amide resin of the component (A) is 20 to 80% by weight, the bromine-containing flame retardant of the component (B) is 10 to 40% by weight, and the zinc-containing composite oxide of the component (C) is 4 to 10% by weight, The antimony-containing compound of component (D) is 0.5 to 3% by weight,
The flame-retardant polyamide resin composition according to claim 1, wherein the total of the components (A) to (D) is 100% by weight.

[4] The composition ratio of the components (A) to (D) and the components (E) and / or (F) is as follows.
Based on the total weight of component (D) and component (E) and / or component (F), the amide resin of component (A) is 2
0 to 80% by weight, the bromine-containing flame retardant of component (B) is 10
-40% by weight, the zinc-containing composite oxide of component (C) is 4
-10 wt%, the antimony-containing compound of component (D),
0.5 to 3% by weight of the fibrous filler of the component (E) is 0.
01-60 wt%, the aliphatic polyamide of component (F),
0.01 to 10% by weight and components (A) to (D)
And the total of component (E) and / or component (F) is 100
The flame-retardant polyamide resin composition as described in [2], which is characterized in that the content is% by weight.

[5] In accordance with ASTM D648,
When the deflection temperature under load (load 1.82 MPa) is evaluated, the deflection temperature under load has a performance of 270 ° C. to 330 ° C., which is the flame retardancy described in any one of [1] to [4]. Polyamide resin composition.

[6] According to UL 94, when vertical combustion (thickness 1/32 inch test piece) is evaluated, the flame retardancy is V-0. [1] ] The flame-retardant polyamide resin composition described in any of [5].

[7] According to UL 746A, when the comparative tracking index is evaluated, the performance level range (PLC) of the comparative tracking index (CTI) has a performance of 0. [1] ] To [9]
The flame-retardant polyamide resin composition described in any one of 1.

[8] A molded article containing the flame-retardant polyamide resin composition according to any one of [1] to [7].

[9] An electric component comprising a molded article containing the flame-retardant polyamide resin composition according to any one of [1] to [7].

[10] An electronic component including a molded article containing the flame-retardant polyamide resin composition according to any one of [1] to [7].

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Polyamide resin, bromine-containing flame retardant, fibrous filler, zinc-containing complex oxide, antimony-containing compound, and aliphatic polyamide which constitute the flame-retardant polyamide resin composition according to the present invention are described below. A specific description will be given, and further, the molded product and the electric / electronic components will be specifically described.

[Polyamide Resin] The repeating unit constituting the molecule of the polyamide resin used in the present invention comprises a repeating unit derived from a diamine and a repeating unit derived from a dicarboxylic acid.

[Diamine-Derived Repeating Unit of Polyamide Resin] The polyamide resin (component (A)) used in the present invention.
The repeating unit derived from diamine is a repeating unit derived from an aliphatic diamine having 6 to 12 carbon atoms.

[Dicarboxylic acid-derived repeating unit of polyamide resin] The dicarboxylic acid-derived repeating unit of the polyamide resin (component (A)) used in the present invention is terephthalic acid based on the total number of moles of all dicarboxylic acid-derived repeating units. It is characterized in that the repeating unit derived from it is 40 to 100 mol%, and the repeating unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms is 0 to 60 mol%.

[Diamine used for producing polyamide resin] The diamine-derived repeating unit of the polyamide resin used in the present invention is derived from the following diamine component. That is, the diamine component used in the production of the polyamide resin used in the present invention contains an aliphatic diamine having 6 to 12 carbon atoms. Specific examples of the linear aliphatic diamine include 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,11-diaminoundecane, And 1,12-diaminododecane can be mentioned. Of these, 1,6-diaminohexane is particularly preferable. Further, the diamine component of the present invention may have a side chain such as a methylene group and an ethylene group, and is 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2- Methyl-1,7
-Diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 2-methyl-1,1
1-diaminoundecane and the like can be mentioned. Among these, 2-methyl-1,5-diaminopentane is particularly preferable. As the diamine component, each of the linear aliphatic diamine component and the aliphatic diamine component having a side chain alkyl group may be used alone, or these diamines can be mixed and used at an arbitrary ratio.

[Dicarboxylic Acid Used in Production of Polyamide Resin] The dicarboxylic acid-derived repeating unit of the polyamide resin used in the present invention is derived from the following dicarboxylic acid component. That is, the dicarboxylic acid component used in the production of the polyamide resin used in the present invention is characterized by comprising 40 to 100 mol% of a terephthalic acid component unit when the dicarboxylic acid component is 100 mol%. Other dicarboxylic acid components that can be used with terephthalic acid include aromatic dicarboxylic acids other than terephthalic acid and / or aliphatic dicarboxylic acids having 4 to 20 carbon atoms. Examples of aromatic dicarboxylic acid component units other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and combinations thereof. The number of carbon atoms of the aliphatic dicarboxylic acid component unit is not particularly limited, but it is preferably 4 to 20, more preferably 6 to.
Derived from 12 aliphatic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid used for deriving such an aliphatic dicarboxylic acid component unit include, for example, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid. Etc. Of these, adipic acid is particularly preferable.

[Ratio of terephthalic acid] In the present invention, when the total amount of dicarboxylic acid constituting the dicarboxylic acid component is 100 mol%, terephthalic acid is 40 to 100.
The constituent unit, which is contained in an amount of mol% and is derived from an aromatic dicarboxylic acid component unit other than terephthalic acid, is 0 to 60 mol% and / or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms. It is preferable that the structural unit derived from the acid component unit is contained in an amount of 0 to 60 mol%. Further, in the present invention, a small amount, for example, about 10 mol% or less of polyvalent carboxylic acid may be contained together with the above dicarboxylic acid. Specific examples of such polycarboxylic acid include tribasic acid and polybasic acid such as trimellitic acid and pyromellitic acid.

[Production of Polyamide Resin] In order to produce the polyamide resin used in the present invention, the above-mentioned diamine component and dicarboxylic acid component are added and heated in the presence of a catalyst. You can
In this reaction, the total number of moles of the diamine component is
It is preferable to add more than the total number of moles of the dicarboxylic acid component, particularly preferably 100 mol of the total dicarboxylic acid component.
When the amount is mol, the total diamine component is 100 to 120 mol. This reaction is usually performed in an inert gas atmosphere, and the inside of the reaction vessel is generally replaced with an inert gas such as nitrogen gas. Further, in order to control the polycondensation reaction of the polyamide, it is desirable to pre-enclose water, and an organic solvent soluble in water, for example, alcohols such as methanol and ethanol may be contained.

[Catalyst] The catalyst used in the production of the polyamide resin (A) used in the present invention includes phosphoric acid, its salts and phosphoric acid ester compounds; phosphorous acid, its salts and ester compounds; Hypophosphorous acid, its salts and ester compounds can be used. Among these, sodium phosphate, sodium phosphite,
Potassium hypophosphite, sodium hypophosphite and the like are preferred. These phosphoric acid compounds can be used alone or in combination. Such a phosphorus compound is usually used in a proportion of 0.01 to 5 mol, preferably 0.05 to 2 mol, per 100 mol of the above dicarboxylic acid.

[End Capping Agent] In order to produce the polyamide resin used in the present invention, it is preferable to use an end capping agent. As the terminal blocking agent, benzoic acid, an alkali metal salt of benzoic acid, acetic acid, or the like can be used. Such an end-capping agent is usually 0.1 to 5 mol, preferably 0.5 to 100 mol, based on 100 mol of dicarboxylic acid.
Used in an amount within the range of 2 moles. The intrinsic viscosity [η] of the obtained polycondensate can be controlled by adjusting the amount of the end-capping agent used.

[Reaction conditions] The reaction conditions for preparing such a polycondensate are, specifically, a reaction temperature of usually 200.
-290 ° C, preferably 220-280 ° C, and the reaction time is generally 0.5-5 hours, preferably 1-3 hours. Further, this reaction can be carried out under any conditions from normal pressure to pressurization, but it is preferable to carry out the reaction under pressurization conditions, and the reaction pressure is usually 2 to 5 MPa, preferably 2.5 to 4
It is set within the range of MPa.

[Intrinsic Viscosity of Polyamide Lower Condensation [η]] By carrying out the polycondensation reaction in this manner,
The intrinsic viscosity [η] measured with a Ubbelohde viscometer in 96.5% sulfuric acid at 25 ° C is usually 0.05 to 0.6.
Low-order condensates in the range of dl / g, preferably 0.08-0.3 dl / g can be obtained. The polyamide low-order condensate thus produced in the aqueous medium is separated from the reaction solution. For separating the polyamide low-order condensate and the reaction solution, for example, a method such as filtration or centrifugation can be adopted, but the reaction solution containing the produced semi-aromatic polyamide low-order condensate is passed through a nozzle. The method of solid-liquid separation by flashing to the atmosphere through is effective.

[Post-Polymerization] In a preferred embodiment of the method for producing the polyamide resin used in the present invention, the polyamide low-order condensate obtained as described above is further post-polymerized. It is preferable that the post-polymerization is carried out by heating the polyamide low-order condensate and then heating it to give a molten state, and applying shear stress to the melt. In this reaction, heating is performed at a temperature at which the dry polyamide low-order condensate is at least melted. Generally, it is heated to a temperature above the melting point of the dry polyamide lower condensate, preferably 10 to 60 ° C. higher than this melting point. Shear stress can be imparted to the melt by using, for example, a vented twin-screw extruder, a kneader or the like. It is considered that by applying shear stress to the melt in this manner, the dry polyamide low-order condensate in the melted state is polycondensed with each other and the polycondensation reaction of the condensate also proceeds.

[Solid Phase Polymerization] In another preferred embodiment of the method for producing a polyamide resin used in the present invention, the polyamide low-order condensate obtained as described above is further subjected to solid phase polymerization. That is, the polyamide low-order condensate obtained as described above is solid-phase polymerized by a known / publicly used method, and the intrinsic viscosity [η] measured by the above method is 0.5 to 2.0 dl. Polyamides in the range of / g can be prepared.

[Melt Polymerization] In another preferred embodiment of the method for producing the polyamide resin used in the present invention, the polyamide low-order condensate obtained as described above is subjected to solid phase polymerization and then melted. Polymerize. That is, the polyamide low-order condensate obtained as described above is subjected to solid-phase polymerization by a known / publicly used method to give a polyamide having an intrinsic viscosity [η] of 0.5 to 1.5 dl / g. The intrinsic viscosity [η] can be adjusted to 0.8 to 3.0 dl / g by preparing a precursor and then melt-polymerizing the precursor. When the intrinsic viscosity is in this range, a polyamide resin having excellent fluidity and high toughness can be obtained.

[DSC] The polyamide resin used in the present invention has a melting point because it is crystalline, and the polyamide resin obtained by the above production method is analyzed by DSC at 10 ° C.
When the endothermic peak due to melting when the temperature is raised at 1 / min is the melting point, the melting point is preferably in the range of 270 to 340 ° C., particularly preferably 280 ° C. to 320 ° C., so that it has excellent heat resistance. it can.

[Molding] The polyamide resin composition according to the present invention can be molded into a desired shape by using a conventional molding device by heating the polyamide resin composition to a temperature above the melting point of the polyamide to be used and below the decomposition temperature. In particular, injection molding enables efficient molding of electric / electronic components.

[Composition Ratio of Polyamide Resin Composition (Four-Component System)] The polyamide resin composition according to the present invention comprises a polyamide resin as the component (A), a bromine-containing flame retardant as the component (B), and a component (C). In a system containing a zinc-containing composite oxide and at least four components containing an antimony-containing compound as the component (D) (four-component system), the composition ratio of the components (A) to (D) is as follows: ) To component (D) based on the total weight of component (A) amide resin 20 to 80 wt%, component (B) bromine-containing flame retardant 10 to 40 wt%, component (C) zinc content It is characterized in that the composite oxide is 4 to 10% by weight and the total of the components (A) to (D) is 100% by weight.

[Composition ratio of polyamide resin composition (5-component system / 6-component system)] The polyamide resin composition according to the present invention comprises a polyamide resin as the component (A), a bromine-containing flame retardant as the component (B), and a component. At least comprising a zinc-containing composite oxide as (C), an antimony-containing compound as component (D), and a fibrous filler as component (E), and / or an aliphatic polyamide as component (F). In a system containing 5 components or 6 components (5 component system, 6 component system), the composition ratio of the components (A) to (D) and the components (E) and / or (F) is as follows: ) To component (D) and, based on the total weight of component (E) and / or component (F), the amide resin of component (A) is 20-80.
% By weight, 10-40% by weight of component (B) bromine-containing flame retardant, 4-10% by weight of component (C) zinc-containing composite oxide, 0.5-3 by weight of component (D) antimony-containing compound. % By weight, 0.01 to 60% by weight of the fibrous filler of component (E), 0.01 to 10% by weight of the aliphatic polyamide of component (F), and components (A) to (D) and Ingredient (E)
And / or the total of the component (F) is 100% by weight.

[Composition Ratio of Polyamide (Component (A)) in Polyamide Resin Composition] In both the 4-component system and the 6-component system, the composition ratio of polyamide in the polyamide resin composition is 20 to 80% by weight. Is preferred and 25 to 50% by weight is particularly preferred. The polyamide resin content is 20
When it is less than 80% by weight, the heat resistance and high toughness of the polyamide resin do not exhibit the effect, and when it exceeds 80% by weight, flame retardancy and rigidity are poor.

[Bromine-Containing Flame Retardant (Component (B))] The polyamide resin composition according to the present invention is characterized by containing a bromine-containing flame retardant, and comprises condensation of brominated polystyrene, brominated phenol and brominated polycarbonate. Items and the like can be used alone or in combination. Among these flame retardants, brominated polystyrene and / or brominated phenol condensate is particularly preferable. The condensate of brominated polystyrene and brominated phenol will be described below.

[Brominated Polystyrene] As the brominated polystyrene used in the present invention, a polymer represented by the general formula (1) is used.

[0042]

[Chemical 1] In the general formula (1), R is H or CH ₃ , and X is B
r, m is a number from 1 to 5, and n has a lower limit of 2, preferably 4, more preferably 8, more preferably 10, and an upper limit of 10, preferably 50, more preferably 100, More preferably 200, more preferably 40
It is a number above 0, more preferably 800, or higher. Polybrominated styrene is particularly preferable as the brominated polystyrene represented by the general formula (1), and polybrominated styrene is one produced by polymerizing brominated styrene or brominated α-methylstyrene. It may be produced by brominating polystyrene or poly α-methylstyrene,
Moreover, you may include both of these. As such polybrominated styrene, specifically, for example, polydibromostyrene, polytribromostyrene, polypentabromostyrene, polytribromoα-methylstyrene, dibromopothistyrene, tribromopolystyrene, tripentapolystyrene, tribromoα. -Methyl polystyrene and the like.

[Condensate of Brominated Phenol] The condensate of halogenated phenol used in the present invention is represented by the following general formula (2).

[0044]

[Chemical 2] In the general formula (2), X is Br, p is a number of 1 to 4, and q has a lower limit of 1, preferably 2, more preferably 5, and an upper limit of 10, preferably 20, and more preferably. Is 4
The number is 0, more preferably 60, more preferably 80, more preferably 100. Specific examples of the condensate of brominated phenol represented by the general formula (2) include polydibromo-p-phenylene oxide and polytribromo-p-.
Examples thereof include phenylene oxide, polybromo-p-phenylene oxide and polydibromo-o-phenylene oxide. Among these bromine-containing flame retardants, brominated polystyrene, and brominated phenol, polydibromostyrene, dibromopolystyrene, polytribromostyrene, tribromopolystyrene are excellent in thermal stability during molding of the composition, It is the most preferable because it has an excellent flame retardant effect.

[Content of Bromine-containing Flame Retardant (Component (B))] Bromine-containing flame retardant (component (B)) used in the present invention
Preferably has a bromine content of 40 to 70% by weight, particularly preferably 50 to 70% by weight. The flame-retardant polyamide resin composition of the present invention preferably contains the bromine-containing flame retardant in an amount of 10 to 40% by weight, particularly 10 to 40% by weight.
It is preferably contained in an amount of 30% by weight. When the content of the bromine-containing flame retardant is less than 10% by weight, the effect of the flame retardant is not exhibited, and when it is more than 40% by weight, the tracking resistance of the flame-retardant polyamide resin composition becomes low.

[Fibrous Filler (Component (E))] The fibrous filler (component (E)) used in the present invention includes, as an inorganic filler, glass fiber, potassium titanate fiber, and metal-coated glass. Examples thereof include fibers, ceramic fibers, wollastonite, metal carbide fibers, hardened metal fibers, asbestos fibers and boron fibers. Further, examples of the organic filler include aramid fiber and carbon fiber.
As such a fibrous filler, glass fiber is particularly preferable. By using glass fibers, the moldability of the composition is improved, and at the same time, mechanical properties such as tensile strength, bending strength, and bending elastic modulus of the molded product formed from the thermoplastic resin composition and heat deformation temperature, etc. Heat resistance is improved. The average length of the fibrous filler as described above is usually 0.01 to
It is in the range of 20 mm, preferably 0.1-6 mm, and the aspect ratio is usually 5-2000, preferably 15-6.
It is in the range of 00. It is preferable to use a fibrous filler having an average length and an aspect ratio within such a range. The fibrous filler in the present invention may be treated with a silane coupling agent or a titanium coupling agent before use. For example, it is preferably surface-treated with a compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltriethoxysilane. Further, the fibrous filler in the present invention may be coated with a sizing agent, and may be epoxy type, urethane type, urethane / maleic acid modified type,
A urethane / amine-modified compound is preferably used. The surface-treating agent may be used in combination with the sizing agent. By using the sizing agent together, the fibrous filler in the composition of the present invention and the other components in the composition are improved in binding property, and the appearance and strength are improved. The characteristics are improved. The flame-retardant polyamide resin composition of the present invention preferably contains the fibrous filler in an amount of 0 to 60% by weight, particularly preferably 10 to 50% by weight. When the content of the fibrous filler is more than 60% by weight, the appearance of the surface of the molded article of the flame-retardant polyamide resin composition is impaired.

[Zinc-Containing Complex Oxide (Component (C))] Specific examples of the zinc-containing oxide (component (C)) used in the present invention include, for example, 2ZnO.3B ₂ O ₃ and 4ZnO.
_{B 2 O 3 · H2O, 2ZnO} · 3B 2 O 3 · 3.5H 2 O,
Zinc borate represented by, ZnSnO ₃ , ZnSn
Examples thereof include zinc stannates represented by (OH) ₆ , calcium zinc molybdate, basic zinc molybdate, compounds of highly efficient zinc molybdate and magnesium silicate, and zinc phosphate.

[Compound containing antimony (component (D))]
Examples of the antimony-containing compound (component (D)) used in the present invention include antimony trioxide, antimony pentoxide, antimony tetroxide, sodium antimonate and the like. The flame-retardant polyamide resin composition of the present invention preferably contains the zinc-containing composite oxide in an amount of 4 to 10% by weight. The antimony-containing compound is contained in an amount of 0.5 to 3% by weight, preferably 0.5 to 2% by weight, particularly preferably 0.5 to 1% by weight. The zinc-containing complex oxide, and the antimony-containing compound content,
When it is less than 4% by weight and 0.5% by weight, the flame retardant effect is not exhibited, and when it is more than 10% by weight and 1% by weight, the tracking resistance of the flame retardant polyamide resin composition is high. Get scarce.

[Aliphatic Polyamide] The flame-retardant polyamide resin composition according to the present invention may contain an aliphatic polyamide. Specific examples thereof include PA6,
PA66, PA11, PA12, PA610, PA61
2, PA46 and the like. The aliphatic polyamide is preferably contained in the flame-retardant polyamide resin composition of the present invention in an amount of 0 to 10% by weight, and when it is contained in this range, strength characteristics of the polyamide resin composition, particularly impact resistance Is improved. When the content of the aliphatic polyamide is more than 10% by weight, the heat resistance of the flame-retardant polyamide resin composition is impaired.

[Other Components] The flame-retardant polyamide resin composition according to the present invention contains, in addition to the above-mentioned components, a heat stabilizer, a weather stabilizer, and a heat stabilizer other than those mentioned above, as long as the object of the present invention is not impaired. Contains compounding agents such as plasticizers, thickeners, antistatic agents, release agents, pigments, dyes, inorganic and / or organic fillers, nucleating agents, carbon black, talc, mica, clay and other inorganic compounds. Good. Further, the flame-retardant polyamide resin composition of the present invention may contain other polymers within the range not impairing the object of the present invention. Examples of such other polymers include polyethylene, polypropylene and poly-4. -Methyl-1-pentene, ethylene / 1-butene copolymer, propylene / ethylene copolymer, propylene / 1
-Butene copolymer, polyolefin such as polyolefin elastomer, polystyrene, polyamide, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesin, silicone resin and the like.

[Molded Product and Electric / Electronic Parts] The flame-retardant polyamide composition according to the present invention comprises the above-mentioned components.
Various known methods, for example, a method of mixing with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or after mixing, after melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, granulation or It can be prepared by using a pulverizing method. Specifically, the polyamide resin in a molten state,
For example, it can be prepared by a method of mixing and kneading the above-mentioned fibrous filler, powdery filler and various additives while heating and maintaining at 280 to 360 ° C. At this time, an ordinary kneading device such as an extruder or a kneader can be used. For example, the polyamide resin composition of the present invention prepared as described above is formed into a powder, a pellet or another shape, and the compression molding method, the injection molding method, the extrusion molding method or the like is used to produce an electric / electronic material. It can be various molded products such as parts and automobile parts. There is no limitation on the molded product, particularly electric / electronic parts, but examples thereof include breakers, contactors, and various connectors.

[0052]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, it measured according to the following method in an Example and a comparative example.

Deflection temperature : measured in accordance with ASTM D648, a bending stress of 1.82 MPa was applied,
The temperature rises at 2 ° C / min and the deflection under load is 0.254 m.
The temperature was measured when the temperature reached m.

Water absorption rate : Measured according to ASTM D570, and a test piece having a thickness of 2 mm was measured at 23 ° C. and 1
It was immersed in water at 00 ° C. for 24 hours, and the water absorption was calculated by the following formula. M = (M2-M1) / M1 × 100 M: Water absorption rate (% by weight) M1: Absolute dry weight of test piece (g) M2: Weight of test piece after water absorption (g) Flame retardancy test : In accordance with UL 94 The flame retardancy was evaluated for the test piece having a thickness of 1/32 inch.

Comparative Tracking Index (CTI) : U
Measured in accordance with L 746A, a test piece having a thickness of 2 mm was subjected to 0.1% NH at 23 ° C. and 50% RH.
CTI was measured at 4 mm between electrodes using a 4Cl aqueous solution. CTI operation level range (PLC) is 600V
In the above case, 0 was set, and in the case of 400 V or more and less than 600 V, 1 was set.

Tensile test : Measured according to ASTM D638, and measured for tensile strength and tensile elongation.

Bending test : The bending strength and bending elastic modulus were measured according to ASTM D790.

IZOD impact strength (with notch) : A
It was measured according to STM D256. [Examples 1 to 3] [Comparative Examples 1 to 3] Component (A) to component (F) The following components were used in the amounts shown in the table, and the total of component (A) to component (F) was used. To 100 parts by weight, maleated SEBS (manufactured by Asahi Kasei Corporation, Tuftec M as an anti-drip agent during combustion)
1913) as a halogen catcher, hydrotalcite (KW-220 manufactured by Kyowa Chemical Co., Ltd.).
0) Add 0.6 parts by weight of each mixture and mix at a temperature of 31
The mixture was charged into an extruder with a twin screw vent set to 0 ° C., melt-kneaded and pelletized to obtain a pellet-shaped flame-retardant polyamide resin composition. [Component (A) -polyamide resin] [Examples 1-2] [Comparative Examples 1-2] Polyamide resin type: PA6T / 66 = 55/45 (molar ratio) Composition: diamine component ... 1,6-diaminohexane 50 Mol%, dicarboxylic acid component ... terephthalic acid 27.5 mol%, adipic acid 22.5 mol% Intrinsic viscosity [η] ... 1.0 dl / g Melting point (DSC method) ... 310 ° C. [Example 3] Polyamide resin type : PA6T / i6T = 50/50 (molar ratio) Composition: Diamine component: 25 mol% of 1,6-diaminohexane, 25 mol% of 2-methyl-1,5-diaminopentane, dicarboxylic acid component: 50 mol% of terephthalic acid Intrinsic viscosity [η] ... 1.0 dl / g Melting point (DSC method) ... 305 ° C. [Comparative Example 3] Polyamide resin type: PA66 Composition: Diamine component ... 1,6-diaminohexane 0 mol%, the dicarboxylic acid component ... adipic acid 50 mol% an intrinsic viscosity [η] ... 1.2 dl / g melting point (DSC method) ... 260 ° C. [component (B) ~ bromine-containing flame retardants] brominated polystyrene (Manac ( Ltd., PLACEFTY 1200Z) [Component (C) -zinc- containing composite oxide] Zinc borate (manufactured by Borax, FireBrake50
0) [Component (D) -antimony-containing compound] sodium antimonate (manufactured by Nippon Seiko Co., Ltd., SA-
A) [Component (F) -aliphatic polyamide] PA12 (Ube Industries, UBE nylon 12) [Component (E) -fibrous filler] Glass fiber (Nippon Electric Glass Co., Ltd., ESC03-61)
5) Next, the properties of the obtained flame-retardant polyamide resin composition were evaluated. The results are shown in the table.

[0059]

[Table 1]

[0060]

The flame-retardant polyamide resin composition according to the present invention contains the above-mentioned components in the above-mentioned specific proportions, and therefore has the following properties: heat resistance, low water absorption, flame retardancy, and Excellent tracking resistance. Therefore, it is preferably used as a material for molding electric / electronic parts. Further, a molded article obtained from such a flame-retardant polyamide resin composition is excellent in flame retardancy and tracking resistance, and thus is suitably used for electric parts used under high voltage.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 71/10 C08L 71/10 F term (reference) 4F071 AA22 AA51 AA55 AB17 AB19 AB26 AB27 AE07 AF10 AF14 AF23 AF45 AF47 AF53 AH07 AH12 AH19 BA01 4J002 BC112 CH062 CL013 CL031 CL033 CL064 DA017 DB007 DE046 DE106 DE127 DE186 DE187 DH046 DJ006 DJ007 DJ027 DK007 DL008 DM007 FA048 FB044 FB077 FB094 FB097 FD014 GQ00

Claims (10)

[Claims] 1. A polyamide resin as the component (A), a bromine-containing flame retardant as the component (B), and a component (C).
A flame-retardant polyamide resin composition comprising a zinc-containing composite oxide and an antimony-containing compound as component (D), wherein the repeating unit constituting the molecule of the polyamide resin of component (A) is a diamine-derived repeating unit. The unit is a repeating unit derived from an aliphatic diamine having 6 to 12 carbon atoms, the repeating unit derived from a dicarboxylic acid is based on the total number of moles of the repeating units derived from all dicarboxylic acids, and the repeating unit derived from a terephthalic acid is 40 to 100. %, And an aromatic dicarboxylic acid-derived repeating unit other than terephthalic acid, and / or an aliphatic dicarboxylic acid-derived repeating unit having 4 to 20 carbon atoms are 0 to 60% by mole, Flammable polyamide resin composition. 2. A polyamide resin as the component (A), a bromine-containing flame retardant as the component (B), and a component (C).
Flame-retardant composition comprising a zinc-containing complex oxide, a component (D), an antimony-containing compound, a fibrous filler as a component (E), and / or an aliphatic polyamide as a component (F). -Forming polyamide resin composition, wherein the repeating unit constituting the molecule of the polyamide resin of the component (A) is a repeating unit derived from a diamine, which is a repeating unit derived from an aliphatic diamine having 6 to 12 carbon atoms, and is derived from a dicarboxylic acid. The repeating unit is based on the total number of moles of all dicarboxylic acid-derived repeating units, the repeating unit derived from terephthalic acid is 40 to 100 mol%, and the repeating unit derived from an aromatic dicarboxylic acid other than terephthalic acid, and / or The repeating unit derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms is 0 to 60 mol%, which is difficult. Flammable polyamide resin composition. 3. The composition ratio of components (A) to (D) is 20 to 80% by weight of the amide resin of component (A), based on the total weight of components (A) to (D). The bromine-containing flame retardant of the component (B) is 10 to 40% by weight, the zinc-containing composite oxide of the component (C) is 4 to 10% by weight, and the antimony-containing compound of the component (D) is 0.5 to 3%. The flame-retardant polyamide resin composition according to claim 1, characterized in that the total amount of the components (A) to (D) is 100% by weight. 4. The composition ratio of the component (A) to the component (D) and the component (E) and / or the component (F) is from the component (A) to the component (A).
Based on the total weight of component (D) and component (E) and / or component (F), the amide resin of component (A) is from 20 to 80% by weight, and the bromine-containing flame retardant of component (B) is 10% by weight. -40% by weight, component (C) zinc-containing composite oxide 4-10% by weight, component (D) antimony-containing compound 0.5-3% by weight, component (E) fibrous filler. Is 0.01 to 60% by weight, the aliphatic polyamide of the component (F) is 0.01 to 10% by weight, and the components (A) to (D) and the component (E) and / or the component (F). The flame-retardant polyamide resin composition according to claim 2, wherein the total of 100% by weight is 100% by weight. 5. When the deflection temperature under load (load 1.82 MPa) is evaluated according to ASTM D648, the deflection temperature under load has a performance of 270 ° C. to 330 ° C. The flame-retardant polyamide resin composition according to any one of 4 above. 6. The flame retardancy is V when the vertical combustion (thickness 1/32 inch test piece) is evaluated according to UL 94.
6. It has a performance of −0.
The flame-retardant polyamide resin composition described in any one of 1. 7. The performance level range (PLC) of the comparative tracking index (CTI) has a performance of 0 when the comparative tracking index is evaluated according to UL 746A. A flame-retardant polyamide resin composition as described in any one of 1 to 6. 8. A molded article comprising the flame-retardant polyamide resin composition according to any one of claims 1 to 7. 9. An electric part comprising a molded article containing the flame-retardant polyamide resin composition according to claim 1. Description: 10. An electronic component including a molded article containing the flame-retardant polyamide resin composition according to claim 1. Description: