JP2002309081A - Polyamide resin composition and electric and electronic part by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having an excellent high electric voltage resistant characteristic. SOLUTION: This polyamide resin composition is characterized by containing (A) 100 pts.wt. polyamide and (B) 15-120 pt.wt. borate salt, and not containing essentially a halogen-based flame retardant, and preferably, further containing (C) 15-150 pt.wt. inorganic filler based on 100 pt.wt. above (A) polyamide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention belongs to the technical field of a polyamide resin composition having a high withstand voltage characteristic and an electric and electronic component using the same, and more specifically, a high tracking resistance is required. The invention belongs to the technical field of a polyamide resin composition suitable for use in an electric / electronic part and an electric / electronic part which is a molded article of the composition.

[0002]

2. Description of the Related Art JP-A-59-189165 discloses that
Glass fiber reinforced polyamide compositions having flame retardancy and arc track resistance are described. This composition contains 16 to 30% by weight of melamine or melamine cyanurate.
1 to 10% by weight of a specific brominated flame retardant, and at least one of zinc oxide, zinc borate, a mixture of zinc oxide and zinc borate, and a mixture of antimony oxide and zinc borate as a synergist. Contains more than 10% by weight. According to this composition, the flame retardancy of UL94 V0 to V1 and DIN5
3480/1972 (KC method) (IEC Publ. 1)
12 (equivalent to the solution A method of (1979)), a material having a tracking resistance of 300 to 425 V is obtained.

[0003]

In recent years, applications of electric and electronic parts have been expanded, and in some fields, higher tracking resistance is required. In such a field, the technology described in the above publication is insufficient. Also, since halogen compounds are used as flame retardants, there is a problem of corrosiveness,
There are problems with application to electrical and electronic components. Furthermore, from the viewpoint of environmental issues, the use of halogen-based flame retardants should be avoided. Flame retardants such as melamine and melamine cyanurate are known as non-halogen flame retardants having no environmental problems, but these flame retardants have relatively low decomposition temperatures,
When contained in a relatively high ratio in the resin composition for molding,
The molding conditions for the resin composition are limited, which is inconvenient in production. In addition, the resin composition containing such a non-halogen flame retardant also has a problem that the appearance of a molded article is likely to be poor, which restricts the expansion of applications.

The present invention has been made in view of the above problems, and provides a polyamide resin composition which can reduce corrosion, is environmentally friendly, has good production suitability, and has excellent high voltage resistance characteristics. That is the task. Another object of the present invention is to manufacture an electric / electronic component having high withstand voltage characteristics.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a resin composition containing a polyamide and a borate in a specific ratio exhibits excellent high voltage resistance characteristics. As a result, the present invention has been completed based on this finding.
That is, in order to solve the above problems, the polyamide resin composition of the present invention comprises:
(B) The composition is characterized in that it contains 15 to 120 parts by weight of a borate and contains substantially no halogen-based flame retardant.

In the present invention, the content of the polyamide and the borate is regulated to the above-mentioned ratio, thereby obtaining a polyamide resin composition having excellent high voltage resistance while maintaining good production suitability. Further, since the polyamide resin composition of the present invention does not contain a halogen-based flame retardant, the problem of corrosion due to the halogen-based compound and the problem of environment are solved.

The polyamide resin composition of the present invention further comprises (C) an inorganic filler and (A) a polyamide 100
It may be contained in an amount of 15 to 150 parts by weight based on parts by weight. The inorganic filler (C) is preferably at least one or two or more selected from glass fibers, metal oxides, metal hydroxides, metal silicate compounds and metal titanate compounds. More preferably, there is. In this specification, "inorganic filler" includes
Borates are not included.

In the polyamide resin composition of the present invention,
The content of the borate (B) is preferably 15 to 95 parts by weight based on 100 parts by weight of the polyamide (A). Further, the borate (B) is preferably zinc borate. It is preferable that the polyamide resin composition of the present invention does not contain a melamine compound.

In the polyamide resin composition of the present invention, IE
C Publ. According to the solution A method of No. 112 (1979), a comparative tracking index (hereinafter abbreviated as BCTI) at the brass electrode can be 800 V or more by measurement using a brass electrode, which is more preferable.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In this specification, “to” indicates a range including numerical values described before and after it as a minimum value and a maximum value, respectively.

The polyamide resin composition of the present invention contains at least a polyamide (A) and a borate (B). (A) Polyamide As the polyamide usable in the present invention, a polyamide obtained by polymerization of a lactam having three or more ring members or a polymerizable ω-amino acid, or polycondensation of a dibasic acid and a diamine is exemplified. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone; hexamethylenediamine, nonamethylenediamine,
Undecamethylenediamine, dodecamethylenediamine,
A polymer obtained by polycondensing a diamine such as meta-xylylenediamine with a dicarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, or glutaric acid; or a copolymer thereof. No. More specifically, nylon 4, 6, 7, 8,
11, 12, 6-6, 6-9, 6-10, 6-11, 6
-12; copolymerized nylon 6 / 6-6, 6/12; copolymer of aromatic nylon 6T (T is terephthalic acid) and aromatic nylon; 6I (I is isophthalic acid) / 6T; nylon and aromatic nylon And 6 / 6T, which is a copolymer of Among them, nylon 6, nylon 6
6, copolymer nylon 6 / 6-6 is preferred. Incidentally, two or more polyamides may be used in combination.

As the relative viscosity (ηrel) of the polyamide used in the present invention decreases, the material strength tends to decrease. On the other hand, as the relative viscosity increases, the fluidity decreases and the moldability and product appearance are reduced. Tend to spoil. Considering both trends, the relative viscosity of the polyamide (concentration in 98% sulfuric acid of 1 according to JIS K 6810)
%, A value measured at a temperature of 25 ° C., and in the present specification, “relative viscosity” means a relative viscosity measured under these measurement conditions) is preferably 2.0 to 5.0, More preferably, it is 2.2 to 4.0. The relative viscosity can be adjusted to a desired range by adjusting the degree of polymerization and the molecular weight of the polyamide.

(B) Borate The (B) borate which can be used in the present invention is a salt of an oxyacid having boron as a central element and is represented by the following formula-1. x (M) in _{n O · yB 2 O 3 ·} zH 2 O Scheme-1 expression -1, x and y represents a positive real number, z is a numerical value range specified by zero or more real or two real Represent. In Formula-1, M represents a metal atom. Examples of M include various metals belonging to transition metals, base metals, and the like, and more specifically, zinc, aluminum, and cobalt. n represents a positive real number that varies according to the valence of M. For example, when M is a monovalent metal ion, n = 2
(That is, M ₂ O), n = M when M is a divalent metal ion
1 (ie, MO).

Preferred examples of the borate include zinc borate, aluminum borate, cobalt borate and the like. Zinc borate is more preferred from the viewpoint of positioning as an industrial product and production cost. sometimes stable _{2ZnO · 3B 2 O 3 · zH} 2 0 (z = 3.3~
3.7) is most preferred. In addition, the said borate may use 2 or more types together.

The polyamide resin composition of the present invention can further contain (C) an inorganic filler. In addition,
As described above, in the present specification, the “inorganic filler” does not include a borate. (C) Inorganic filler In the present invention, the inorganic filler is not particularly limited, and various inorganic fillers can be used. The form is not particularly limited, and powder, fiber, and flake forms can be used. Specifically, fibrous fillers represented by glass fibers; zinc oxide,
Metal oxides such as magnesium oxide, calcium oxide, alumina, silicon oxide and titanium oxide; metal hydroxide compounds such as magnesium hydroxide and aluminum hydroxide; talc;
Metal silicates such as kaolin and wollastonite; metal titanate compounds such as potassium titanate and aluminum titanate; Among them, it is preferable to use a glass fiber filler. Two or more of these materials may be used in combination.

The polyamide resin composition of the present invention contains 15 to 120 parts by weight of the borate (B) based on 100 parts by weight of the polyamide (A). (B) Component is 1
When the amount is less than 5 parts by weight, the high voltage resistance becomes insufficient,
On the other hand, if it exceeds 120 parts by weight, it is disadvantageous in terms of cost, and melt kneading becomes difficult. In the present invention, by defining the contents of the components (A) and (B) within the above range, a polyamide resin composition having excellent high voltage resistance while maintaining good production suitability is obtained. The content of the component (B) is 15 to 9 with respect to 100 parts by weight of the component (A).
It is preferably 5 parts by weight, more preferably 20 to 35 parts by weight.

It is preferable that the polyamide resin composition of the present invention contains the inorganic filler component (C) because good mechanical strength can be exhibited. On the other hand, when the content ratio of the component (C) is high, the polyamide resin composition has high resistance to high resistance. Voltage characteristics may be impaired.
From such a viewpoint, in the embodiment containing the component (C),
The content of the component (C) is preferably 15 to 150 parts by weight, and more preferably 20 to 1 part by weight based on 100 parts by weight of the component (A).
More preferably, the amount is 00 parts by weight.

The polyamide resin composition of the present invention is characterized by being substantially free of halogen-based flame retardants. Since the polyamide resin composition of the present invention does not contain a halogen-based flame retardant, the problem of corrosion due to the halogen-based compound and the problem of environment are solved. Furthermore, the polyamide resin composition of the present invention does not have a remarkable decrease in tracking resistance due to containing a halogen compound.

The polyamide resin composition of the present invention preferably does not contain melamine compounds such as melamine and melamine cyanurate. Without the melamine compound, the frequency of occurrence of defective appearance can be further reduced,
In addition, the molding conditions are also preferred because restrictions can be eliminated, and a resin composition having better production suitability can be obtained.

The polyamide resin composition of the present invention contains mechanical properties, dimensional stability, chemical resistance, flame retardancy, heat stability, moldability, weatherability, as long as the objects and effects of the present invention are not impaired. Various thermoplastic resins and / or additives can be contained for the purpose of properties and the like. Examples of various thermoplastic resins include LCP (liquid crystal polymer), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PC (polycarbonate), and modified PPE.
(Polyphenylene ether), PE (polyethylene),
Examples include PP (polypropylene) and PS (polystyrene). Examples of the additives include impact modifiers such as olefin-based elastomers, lubricants such as fatty acid amides, heat stabilizers such as copper compounds and hindered phenols, as well as weather modifiers and coloring agents. When the polyamide resin composition of the present invention contains a resin other than the polyamide (A), the content is preferably 100 parts by weight or less and 0.001 part by weight or more based on 100 parts by weight of the component (A). preferable. When the polyamide resin composition of the present invention contains additives other than the components (A), (B) and (C), the content is 50 parts by weight or less based on 100 parts by weight of the component (A). It is preferably 0.001 part by weight or more.

The polyamide resin composition of the present invention can be prepared according to any of the general methods for preparing a resin composition. For example, a batch blending method in which all components are blended, melt-kneaded by a screw-type extruder, and pelletized, a partial blend in which some components are supplied from another supply port and melt-kneaded with other components to be pelletized. It can be produced by a method or the like. When the composition of the present invention contains the above-mentioned additives and the like, the additives and the like can be blended at any stage of the production process, but it is preferable to melt-knead them with an extruder.

The polyamide resin composition of the present invention has excellent high voltage resistance characteristics. The high withstand voltage characteristics can be evaluated by various methods. The polyamide resin composition of the present invention is an IEC P which is one of the methods for evaluating tracking resistance.
ubl. 112 (1979), it is possible to evaluate the high withstand voltage characteristics in accordance with the solution A method. The polyamide resin composition of the present invention can be obtained from IEC Publ. 112 (1979)
It is preferable that the comparative tracking index (hereinafter abbreviated as BCTI) at the brass electrode is 800 V or more in the measurement using a brass electrode according to the solution A method described above. IEC Publ.
112 (1979), the electrode used is usually a platinum electrode, and the comparative tracking index in this case is referred to as "CTI". The value of BCTI is a value measured by replacing this platinum electrode with a brass electrode. In addition, IE
C Publ. 112 (1979), the upper limit of the test voltage is usually set to 600 V.
The value of TI is a value measured by setting the upper limit of the test voltage to 1000V. In general, when a brass electrode is used, metal ions are eluted from the electrode during the test, as compared with the case where a platinum electrode is used. This is a strict test. Therefore, the IEC Pub using a brass electrode instead of the platinum electrode employed in the present invention and raising the upper limit of the test voltage was used.
l. The test method based on the solution A method 112 (1979) can be said to be a method suitable for evaluating high withstand voltage characteristics.

Hereinafter, IEC Publ. 112 (19
The detailed conditions of the test using a brass electrode according to the solution A method of 79) are shown. Electrode: Brass Distance between electrodes: 4 ± 0.1 mm Applied voltage: 100-1000 V Drop constant: 51 drops Electrolyte: Solution A Ammonium chloride 0.1 ±
0.002% aqueous solution Judgment: When a current of 0.5 A or more flows between the electrodes for 2 seconds or more, or when the sample burns, it is considered to be broken. The maximum voltage that does not destroy is compared with the tracking index (B
CTI).

Since the polyamide resin composition of the present invention has high withstand voltage characteristics, it is useful as an insulator and an electric and electronic part as a molded article having insulating properties. By molding the polyamide resin composition of the present invention, various electric and electronic parts can be manufactured. There is no particular limitation on the molding method of the polyamide resin composition of the present invention,
Various molding methods such as injection molding, extrusion molding, compression molding, blow molding, gas injection molding, transfer molding, two-color molding, and vacuum molding can be used. An appropriate molding method can be selected according to the type, shape, and size.

[0025]

The present invention will be described more specifically with reference to the following examples. Materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Polyamide resin compositions having the compositions shown in Tables 1 and 2 below were prepared. Specifically, each material having the composition shown in Tables 1 and 2 was subjected to a cylinder temperature of 240 using a twin screw extruder “TEX30HCT” manufactured by Nippon Steel Corporation.
２270 ° C., extruded at a screw rotation speed of 200 rpm, and pelletized. After that, 12
After drying at 0 ° C for more than 5 hours, injection molding machine manufactured by Nippon Steel Corporation
Injection molding was performed using J75ED at a resin temperature of 250 ° C. As a molded product for tracking resistance test, 50mmφ, thickness 3
It was formed into a disk-shaped test specimen of mm. The meanings of the abbreviations of the materials in Tables 1 and 2 are as shown in Table 3.

Next, the tracking resistance of each of the molded test articles was evaluated. In addition, after each test piece was molded,
Until the evaluation, the sample was stored in a moisture-proof bag to avoid moisture absorption. The test was performed according to IEC Publ. This is a test using a brass electrode in accordance with the solution A method of No. 112 (1979), and the details of the conditions are as described above. Tables 1 and 2 show the obtained BCTI values.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

According to the present invention, the possibility of corrosion is low,
It is possible to provide a polyamide resin composition which is environmentally friendly, has good production suitability, and has excellent high voltage resistance characteristics. Further, according to the present invention, it is possible to provide an electric / electronic component having excellent high withstand voltage characteristics.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/30 H01B 3 / 30N H01L 23/29 H01L 23/30 R 23/31 (72) Inventor Nakata Michio 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in Mitsubishi Engineering-Plastics Corporation Technical Center (reference) 4J002 CL001 CL011 CL031 CL051 CL061 DE017 DE077 DE087 DE107 DE137 DE147 DE187 DJ017 DJ037 DJ047 DK006 DL007 FA047 FD017 FD136 GQ01 4M109 AA01 CA21 CA22 EA08 EB02 EB07 EB12 EB18 EC07 EC14 EC15 5G305 AA14 AB04 AB25 AB35 BA15 CA20 CC02 CC03 CC11 CC14 CD01

Claims (9)

[Claims] 1. A polyamide resin composition comprising (A) 100 to 100 parts by weight of a polyamide, (B) 15 to 120 parts by weight of a borate, and substantially free of a halogen-based flame retardant. object. 2. An inorganic filler (C) is added to the polyamide (A) in an amount of 15 to 150 parts by weight based on 100 parts by weight of the polyamide.
The polyamide resin composition according to claim 1, which is contained in parts by weight. 3. The method according to claim 1, wherein the inorganic filler (C) is glass fiber,
At least one or two selected from metal oxides, metal hydroxides, metal silicate compounds and metal titanate compounds
The polyamide resin composition according to claim 2, wherein the composition is at least one kind. 4. The polyamide resin composition according to claim 2, wherein the inorganic filler (C) is glass fiber. 5. The polyamide resin composition according to any one of claims 1 to 4, wherein the borate (B) is contained in an amount of 15 to 95 parts by weight based on 100 parts by weight of the polyamide (A). object. 6. The polyamide resin composition according to claim 1, wherein the borate (B) is zinc borate. 7. The polyamide resin composition according to claim 1, which does not contain a melamine compound. 8. IEC Publ. 112 (1979)
According to the solution A method of the above, a comparative tracking index (hereinafter abbreviated as BCTI) with a brass electrode of 8 was measured using a brass electrode.
The polyamide resin composition according to any one of claims 1 to 7, wherein the voltage is 00 V or more. 9. An electric / electronic part comprising the polyamide resin composition according to claim 1. Description: