JPH1126060A - Connector with polyamide resin hinge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a connector with a polyamide resin hinge which is superior in nonflammability, hinge property heat resistance, and rigidity by blending a specific quantity of a triazine flame retarder to a polyamide resin, constituted of a polyamide 66 resin and a polyamide 6 resin at a specific ratio. SOLUTION: A triazine flame retarder (cyanuric acid, isocynuric acid, or melamine) 2-20 pts.wt. is blended to a polyamide resin 100 pts.wt., constituted of a polyamide 66 resin 90-50 wt.% and a polyamide 6 resin 10-50 wt.%, and a connector with a polyamide resin hinge is manufactured from a polymide resin composition thus obtained. The polyamide 66 resin preferably contains a polyamide forming unit 100-95 wt.% constituted of adipic acid and hexamethylenediamine. The relative viscosities of the polyamide resin and the polyamide 6 resin are set to 2.2-3.5 and 2.0-4.5, measured at a temperature of 25 deg.C and at a concentration of 1% in 98%-sulfuric acid in accordance with JIS K6810.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hinged connector made of polyamide resin, and more particularly to a flame-retardant polyamide resin hinged connector.

[0002]

2. Description of the Related Art Connectors are used as devices for connecting electric / electronic circuits between electric devices or inside the devices.
It is widely used in the fields of communication equipment, OA equipment, computers, car electronics equipment, and the like, and has a wide variety of types, and various resin connectors including polyamide resin connectors are used. Among them, the use of hinged connectors, which have the function of assisting in joining wires and combining wires, makes it possible to combine connectors more easily than before.Hinged connectors will continue to be used with the advancement of equipment. It is in the direction of increasing.

When the connector has a hinge portion, when polyamide 6 is used as the connector material, the hinge properties are excellent, but the melting point is low, the compound melts or deforms at a high temperature, and the connector is soldered. Difficult to use. In a field requiring such heat resistance, a connector made of polyamide 66 is usually used. However, in the case of a connector having a hinge shape, there is a problem that hinge properties are not sufficient. Further, as a material that can be used in the field where flame retardancy is required, a resin composition for connectors in which melamine cyanurate is blended with polyamide having a melting point of 255 to 264 ° C. is disclosed in JP-A-8-34918. However, when a hinged connector is made using such a resin composition, the hinge property is insufficient.

[0004] As a method of improving the hinge property, for example, a molded product with a hinge made of polyamide having a melting point of 254 to 264 ° C is disclosed in JP-A-61-229540. However, when a flame retardant is added to such a polyamide in order to impart flame retardancy, the hinge properties of the hinged connector are insufficient.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide resin hinged connector which is excellent in flame retardancy, rigidity and heat resistance and excellent in hinge properties.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem.
Polyamide resin 100 comprising 50 to 50% by weight of polyamide 66 resin and 10 to 50% by weight of polyamide 6 resin
The present invention resides in a polyamide resin hinged connector made of a polyamide resin composition in which 2 to 20 parts by weight of a triazine-based flame retardant is blended in parts by weight.

Hereinafter, the present invention will be described in detail. Examples of the polyamide 66-based resin in the present invention include polyamide 66-based resins containing 100 to 95% by weight, preferably 100 to 96% by weight, of a polyamide-forming unit composed of adipic acid and hexamethylenediamine. Examples of the polyamide-forming component other than the polyamide-forming unit composed of adipic acid and hexamethylenediamine include, for example, a polyamide-forming unit composed of ε-caprolactam. Specific examples of the polyamide 66 resin in the present invention include, for example, a polyamide 66 resin, a polyamide-forming unit composed of adipic acid and hexamethylenediamine, and
And a polyamide 66/6 copolymer containing 0.0095 to 95% by weight. From the viewpoint of heat resistance, polyamide 66/6 is preferred.
Resins.

[0008] The relative viscosity of polyamide 66 resin is determined by JI
According to SK6810, it is a value measured at a concentration of 1% in 98% sulfuric acid and a temperature of 25 ° C., preferably 2.2 to 3.5. When the relative viscosity is less than 2.2, the hinge property tends to decrease, and when the relative viscosity exceeds 3.5, the flame retardancy tends to deteriorate. The relative viscosity of the polyamide 66 resin is more preferably from 2.3 to
3.0.

The amount of the polyamide 66 resin is 90 to 50% by weight of the polyamide resin composed of the polyamide 66 resin and the polyamide 6 resin. When the amount of the polyamide 66-based resin exceeds 90% by weight, the hinge property is reduced,
If it is less than 50% by weight, the moldability tends to decrease. The blending amount of the polyamide 66-based resin is preferably 85 to 55% by weight from the viewpoint of the balance between hinge properties and moldability.

The polyamide 6 resin in the present invention is a polyamide 6 resin obtained by polycondensation using ε-caprolactam as a raw material. The relative viscosity of the polyamide 6 resin is a value measured at a concentration of 1% in 98% sulfuric acid and a temperature of 25 ° C. according to JIS K6810.
0 to 4.5. If the relative viscosity is less than 2.0, the mechanical properties tend to deteriorate, and if it exceeds 4.5, the flame retardancy tends to be impaired. The relative viscosity of the polyamide 6 is more preferably 2.2 to 3.5.

The compounding amount of the polyamide 6 resin is 10 to 50% by weight of the polyamide resin composed of the polyamide 66 resin and the polyamide 6 resin. When the compounding amount of the polyamide 6 resin is less than 10% by weight, the hinge property tends to be reduced.
If the content exceeds 0% by weight, the moldability tends to decrease. The blending amount of the polyamide 6 resin is preferably 15 to 45 parts by weight from the viewpoint of a balance between hinge properties and moldability.

The triazine-based flame retardant of the present invention includes a compound represented by the following general formula (1) or (2):
Melamines and melamine cyanurate are exemplified.

[0013]

Embedded image

(Wherein, R ^{1 to} R ⁶ each represent a hydrogen atom or an alkyl group.)

Specific examples of the compound represented by the general formula (1) include cyanuric acid, trimethyl cyanurate, triethyl cyanurate, tri (n-propyl) cyanurate, methyl cyanurate, diethyl cyanurate and the like. . Specific examples of the compound represented by the general formula (2) include isocyanuric acid, trimethyl isocyanurate, triethyl isocyanurate, tri (n-propyl) isocyanurate, diethyl isocyanurate, and methyl isocyanurate. .

Examples of the melamines include melamine, melamine derivatives, compounds having a structure similar to melamine, condensates of melamine, and the like. Specific examples of melamines include, for example, melamine, ammelide, ammeline,
Formoguanamine, guanylmelamine, cyanomelamine, arylguanamine, melam, melem, melon and the like.

The melamine cyanurate includes an equimolar reaction product of cyanuric acid and melamine. Some of the amino groups or hydroxyl groups in melamine cyanurate may be substituted with other substituents. Melamine cyanurate can be obtained, for example, by mixing an aqueous solution of cyanuric acid and an aqueous solution of melamine, reacting the mixture under stirring at 90 to 100 ° C., and filtering the resulting precipitate to obtain a white solid. It is preferable to use by pulverizing on a powder. Of course, a commercially available product can be used as it is, or it can be used after being crushed.

Preferred examples of the triazine-based flame retardant include cyanuric acid, isocyanuric acid, melamine, melamine cyanurate, and the like. The triazine-based flame retardant is more advantageous because there is no inconvenience such as blooming in which a decomposition product emerges on the surface of a molded product. Preferably, melamine cyanurate is used.

The compounding amount of the triazine-based flame retardant is 90 to 5
It is 2 to 20 parts by weight based on 100 parts by weight of a polyamide resin composed of 0% by weight of a polyamide 66 resin and 10 to 50% by weight of a polyamide 6 resin. If the blending amount of the triazine-based flame retardant is less than 2 parts by weight, the flame retardancy tends to decrease,
If the amount exceeds 20 parts by weight, the hinge property is reduced. The amount of the triazine-based flame retardant is preferably 3 to 15 parts by weight from the viewpoint of the balance between flame retardancy and hinge properties.

As a method of blending the triazine-based flame retardant with the polyamide resin, it can be carried out by any of various well-known means at an arbitrary stage immediately before molding a final molded article. The simplest method is a method in which a polyamide resin and a triazine-based flame retardant are simply dry-blended, and the resulting dry-blended product is pelletized by melt-mixing extrusion.
As another method, the polyamide resin composition according to the present invention may be prepared by previously preparing a master pellet in which a triazine-based flame retardant larger than a predetermined amount is kneaded with a polyamide resin, and dry-blending the master pellet with a polyamide resin for dilution. Can be obtained.

Further, a pigment,
Dyes, fillers, nucleating agents, release agents, stabilizers, antistatic agents and other well-known additives can be blended and kneaded. In particular, a releasing agent such as ethylenebisstearylamide or a releasing agent such as a metal salt of an aliphatic carboxylic acid having 22 to 30 carbon atoms is added, for example, to 0.00100 parts by weight of the polyamide resin.
Mixing about 1 to 2 parts by weight is flame retardant, hinged,
It is preferable because the productivity of the hinged connector can be increased without lowering the rigidity and the heat resistance.

In producing the polyamide resin hinged connector of the present invention, the dry blend and the pellets are supplied to various molding machines such as an injection molding machine, and molded in a conventional manner. FIG. 3 shows an example of a hinged connector made of a polyamide resin. The polyamide resin hinged connector has a function of inserting a plurality of wires into the connector, and the connector into which the wires are inserted is used by bending the hinge portion, fitting the fitting portion, and fixing the wire. .
The shape shown in FIG. 3 is an example of the polyamide hinged connector of the present invention, and may be a hinged connector having a shape and function other than those shown in FIG.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. The evaluation of flammability, hinge properties, rigidity and heat resistance in the following Examples and Comparative Examples was performed according to the following methods. (1) Combustion test: A test specimen having a size of 5 x 1/2 x 1/16 (inch) was used in accordance with the test method UL-94 standard.

(2) Evaluation of Hinge Property: Molded product of hinge test piece type shown in FIG. 1 and FIG.
m, thickness of hinge part 0.3mm) by Toshiba Machine Industry Co., Ltd.
Cylinder temperature 270 ° C, mold temperature 80 ° C, measuring stroke 15mm, injection holding pressure switching position 0mm, injection pressure 25%, injection speed 99 using an IS80EPN injection molding machine
%, Injection time 2 seconds, cooling time 30 seconds, pause time 1 second. Thereafter, the molded product was allowed to stand for 8 hours or more in a completely dried state at 23 ° C., and the hinge was bent at 90 ° in less than 1 second, and the number of hinges of 100 sheets was evaluated. It should be noted that the smaller the number of hinge breaks, the better the hinge properties.

(3) Rigidity: The flexural modulus is determined by ASTM-D7.
The stiffness was evaluated by measuring according to No. 90. . (4) Heat resistance evaluation: The heat resistance was evaluated by measuring the melting point. In the present invention, the melting point is defined as 1 mg of a sample using DSC20 manufactured by Seiko Denshi Kogyo KK.
It refers to the polyamide melting peak temperature when the temperature is raised at 0 ° C./min. (5) Hinge properties of the hinged connector: After the hinged connector shown in FIG. 3 is molded and left in a dry state at 23 ° C. for 8 hours or more, the hinge is bent at 90 degrees in less than 1 second, and the fitting portion A is formed. The evaluation was made based on the number of 100 hinge breaks when the fitting portion B and the fitting portion B were fitted together.

(6) Removability of connector with hinge: FIG.
After the hinged connector shown in Fig. 3 was left in an absolutely dry state at 23 ° C for 8 hours or more after molding, the hinge was bent at 90 ° to fit the fitting portions A and B, and the quality of the touch at the time of insertion and the fitting portion were good. Twenty evaluations were made as to whether or not 抜 け came out by hand.
When the insertion force is low, if the fitting portion comes off, the connector does not perform its original performance as a joining component. In this evaluation, the higher the insertion force and the more difficult it is to pull out, the better the detachability, but at the same time, the higher the detachability in this evaluation, the higher the rigidity of the resin, which means that the connector body has the required rigidity. ing.

(7) Solder heat resistance of hinged connector: A low-temperature solder (230 ° C.) was pressed against the connector shown in FIG. 3 for 10 seconds to test whether the connector melted or deformed. It means that the solder heat resistance is so high that the shape change such as melting and deformation does not occur, and that the heat resistance of the resin itself is high.

The raw materials used in the examples and comparative examples are as follows. (8) Polyamide 66 resin: nylon 66, grade name FE3218, relative viscosity 2.8, manufactured by DuPont. (9) Polyamide 6 resin: nylon 6, grade name 10
10J, relative viscosity 2.5, manufactured by Mitsubishi Chemical Corporation.

(10) Copolyamide 66/6 resin
1: An equimolar salt of hexamethylenediamine-adipic acid and ε-caprolactam were mixed at a ratio of 97/3, charged into a reactor, and polymerized. Nylon 66/6 having a relative viscosity of 2.8.
Copolymer. (11) Copolymerized polyamide 66/6 resin-2: Equimolar salt of hexamethylenediamine-adipic acid and ε-caprolactam were mixed at a ratio of 85/15, charged into a reactor and polymerized to have a relative viscosity of 2.8. Nylon 66/6 copolymer.

(12) Melamine cyanurate: MCA-C
O, manufactured by Mitsubishi Chemical Corporation. (13) Pyro Check 68PB: Brominated polystyrene, manufactured by Ferro. (14) Hostalub NAV101: sodium montanate,
Made by Hoechst Japan Co., Ltd.

[Examples 1 to 5] At the compounding amounts shown in Table 1,
After blending the polyamide resin and various additives, a TEX30C type twin screw extruder manufactured by Nippon Steel Corp.
Was melt-mixed at the set temperature to obtain pellets of the polyamide resin composition. The obtained pellets were injection-molded according to the respective molded articles, and evaluated for flammability, hinge properties, rigidity and heat resistance. Table 1 shows the evaluation results.

[0032]

[Table 1]

[Comparative Examples 1 to 5]
After blending the polyamide resin with various additives, pellets of the polyamide resin composition were obtained in the same manner as in Example 1. Various evaluations were performed on the obtained pellets in the same manner as in Example 1. Table 2 shows the evaluation results.

[0034]

[Table 2]

Comparative Examples 6 to 10 After blending the polyamide resin and various additives in the amounts shown in Table 3, pellets of the polyamide resin composition were obtained in the same manner as in Example 1. Various evaluations were performed on the obtained pellets in the same manner as in Example 1. Table 3 shows the evaluation results.

[0036]

[Table 3]

Example 6 Using pellets having the same formulation as in Example 2, an IS80EP manufactured by Toshiba Machine Industry Co., Ltd.
Using an N injection molding machine, cylinder temperature 270 ° C, mold temperature 80 ° C, measuring stroke 30mm, injection holding pressure switching position 0
mm, injection pressure 25%, injection speed 99%, injection time 2
Molding under the conditions of seconds, cooling time 30 seconds, pause time 1 second,
The molded product of the connector with hinge shown in FIG. 3 (the thickness of the molded product is 0.8 mm, the bottom surface is 20 mm × 25 mm, the interval from the bottom surface to the surface with the hinge portion is 20 mm, 20 mm). The molded product of the hinged connector obtained was evaluated for hinge properties, detachability, and solder heat resistance. Table 4 shows the evaluation results.
Shown in

Comparative Examples 11 to 13 Comparative Examples 1, 9, and 10
Using pellets having the same composition as in Example 1, molding was performed in the same manner as in Example 6, to obtain a molded product of a hinged connector. Hinge property, detachability,
The solder heat resistance was evaluated. Table 4 shows the evaluation results.

[0039]

[Table 4]

[0040]

The hinged connector made of a polyamide resin according to the present invention is excellent in flame retardancy, hinge properties, heat resistance and rigidity, and is useful as a connector for electric / electronic or automotive applications. .

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a molded product used in evaluation of hinge properties.

FIG. 2 is an explanatory view showing a hinge portion of a molded product used in evaluation of hinge properties.

FIG. 3 is an explanatory view showing an example of a hinged connector.

FIG. 4 is an enlarged view of a hinge portion of the hinged connector of FIG. 3;

[Explanation of symbols]

 a 15 mm b 30 mm c 40 mm d, g 1 mm e, f 1.6 mm h 0.3 mm i Fitting part A j Hinge part A k Hinge part B 1 Fitting part B m 0.8R n, p 0.5R o 1 .1R

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Masami Suzuki 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering Plastics Co., Ltd. Technology Center

Claims (5)

[Claims] 1. A polyamide resin comprising 90 to 50% by weight of a polyamide 66 resin and 10 to 50% by weight of a polyamide 6 resin, 100 parts by weight of a polyamide resin,
A hinged connector made of a polyamide resin comprising a polyamide resin composition containing 20 parts by weight. 2. The polyamide 66 resin has a relative viscosity of J
The polyamide resin hinged connector according to claim 1, wherein the value measured at a temperature of 25 ° C and a concentration of 98% sulfuric acid of 1% according to IS K6810 is 2.2 to 3.5. 3. The polyamide 6 resin has a relative viscosity of JIS.
According to K6810, concentration 1% in 98% sulfuric acid, temperature 2
The polyamide resin hinged connector according to claim 1 or 2, wherein the value measured at 5 ° C is 2.0 to 4.5. 4. The polyamide 66-based resin according to claim 1, wherein the polyamide 66-based resin is a polyamide 66-based resin containing 100 to 95% by weight of a polyamide-forming unit composed of adipic acid and hexamethylenediamine. The hinged connector made of the polyamide resin described in the above. 5. The method according to claim 5, wherein the polyamide 66 resin is polyamide 6
The hinged connector made of a polyamide resin according to any one of claims 1 to 3, wherein the connector is a 6-resin.