JP2015159035A - Fuse housing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuse housing which exhibits excellent heat resistance and transparency after securing sufficient arc resistance, and furthermore has excellent productivity caused by excellent flowability of a raw material.SOLUTION: Disclosed is a fuse housing which covers a pair of metal terminals connected by a fuse element and has insulation properties. The fuse housing includes a polyamide resin. The polyamide resin is a copolymer and/or a mixture of aromatic polyamide A and aromatic polyamide B. The mass ratio (A/B) between the aromatic polyamide A and the aromatic polyamide B is 95/5 to 60/40.

Description

  The present invention relates to a fuse housing.

  In general, harnesses arranged from various vehicle electrical components are collected in a fuse box and connected to a battery via a fuse element having a rated current value corresponding to each purpose of use. The fuse element includes a resin housing and a pair of metal terminals. When a current exceeding the rated value flows for some reason, the fusible member connecting the metal terminals is melted to prevent overcurrent from continuing to flow through the electrical component.

  Conventionally, polysulfone and polyethersulfone excellent in heat resistance, insulation, and transparency have been used as a resin housing material. In recent years, the amount of in-vehicle electrical components mounted has increased as electronic control has progressed with improvements in safety and comfort of automobiles. Therefore, not only the conventional 14V power supply system but also a boosted system is required. In the case of a boosted system, the arc generated when the fusible element installed in the fuse element is blown out is larger than in the case of the 14V system. Resulting in. As a result, even if the fusible material is melted, the leakage current flows through the carbonized housing, so that the fuse element itself may be melted or other fuse elements may be damaged. Thus, when applying polysulfone or polyethersulfone as a fuse housing of a boosted system, the arc resistance is not sufficient.

  In order to solve this problem, an aliphatic polyamide resin to which swellable fluoromica or montmorillonite dispersed on a molecular level based on a copolymer and / or blend of polyamide 66 and polyamide 6 is added has been proposed (for example, Patent Literatures 1 to 3). Furthermore, from the viewpoint of dealing with smaller fuses in the 42V power supply system, an aliphatic polyamide resin having improved heat resistance by defining the aspect ratio and amount of GF (glass fiber) has also been proposed (for example, , See Patent Document 4).

International Publication No. 2002/085984 JP 2003-123617 A Japanese Patent No. 4104817 Japanese Patent No. 4433515

  However, the aliphatic polyamides described in Patent Documents 1 to 4 are inferior in transparency as compared to polysulfone and polyethersulfone. Therefore, the visibility for judging visually that the fusible body has melted is lacking. Furthermore, in the molding production of multi-type and multi-piece fuse housings that are color-coded for each rated current value, the technologies described in Patent Documents 1 to 4 are improved in terms of production efficiency in order to meet the cost reduction requirements of automobile manufacturers. It can be said that there is room. That is, in the techniques of Patent Documents 1 to 4, a fuse that exhibits excellent heat resistance and transparency while ensuring sufficient arc resistance, and also has excellent productivity due to good fluidity of raw materials. The housing material cannot be obtained.

  The present invention has been made in view of the above-described problems of the prior art, and after ensuring sufficient arc resistance, exhibits excellent heat resistance and transparency, and further improves the flowability of raw materials. It is an object of the present invention to provide a fuse housing having excellent productivity.

  As a result of intensive investigations, the inventors have improved heat resistance, transparency, and molding fluidity by optimally blending a semi-aromatic polyamide within a range that does not impair the required arc resistance. The present inventors have found that the above problems can be solved and have reached the present invention.

That is, the present invention is as follows.
[1]
A fuse housing that covers a pair of metal terminals connected by a fusible body and has an insulating property,
Including polyamide resin,
The polyamide resin is a copolymer and / or a mixture of an aliphatic polyamide A and an aromatic polyamide B;
The fuse housing whose mass ratio (A / B) of the said aliphatic polyamide A and the said aromatic polyamide B is 95 / 5-60 / 40.
[2]
The fuse housing according to [1], wherein the aromatic polyamide includes polyamide 6I.
[3]
The fuse housing according to [1] or [2], wherein the aliphatic polyamide includes polyamide 66.
[4]
The polyamide resin has at least one melting point and at least one solidification temperature, at least one melting point Tm is 255 ° C. ≧ Tm ≧ 200 ° C., and at least one solidification temperature Tc is 220 ° C. The fuse housing according to any one of [1] to [3], wherein ≧ Tc ≧ 170 ° C.
[5]
The fuse housing according to any one of [1] to [4], further including 1 to 30 parts by mass of an inorganic filler with respect to 100 parts by mass of the polyamide resin.
[6]
The fuse housing according to [5], wherein the inorganic filler includes a layered silicate dispersed at a nano level.
[7]
The fuse housing according to [5] or [6], wherein the inorganic filler includes apatite and is dispersed so that 30% or more of the particle interface of the apatite is in contact with the polyamide resin.
[8]
The fuse housing according to any one of [5] to [7], wherein the inorganic filler includes a glass filler.

  The fuse housing of the present invention exhibits excellent heat resistance and transparency while ensuring sufficient arc resistance, and further has excellent productivity due to good flowability of raw materials.

  Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The fuse housing of this embodiment covers a pair of metal terminals connected by a fusible body and has an insulating property. Moreover, the fuse housing of this embodiment contains a polyamide resin. The polyamide resin is a copolymer and / or a mixture of aliphatic polyamide A and aromatic polyamide B, and the mass ratio (A / B) of aliphatic polyamide A to aromatic polyamide B is 95 / 5-60. / 40. Since it is configured in this manner, the fuse housing of this embodiment exhibits excellent heat resistance and transparency while ensuring sufficient arc resistance, and further excellent due to the good fluidity of the raw material. Has high productivity. Thus, the fuse housing of this embodiment can have good transparency and productivity without impairing the characteristics of a conventional automotive fuse element. That is, the fuse housing of the present embodiment improves the visibility of the fusible melted portion by improving the transparency while maintaining the arc resistance and heat resistance necessary for the automotive fuse housing, and the molding flow By improving the productivity, it is possible to improve the molding productivity of multi-product and multi-piece production and contribute to cost reduction.

(Polyamide resin)
The polyamide resin in the present embodiment is a copolymer and / or a mixture of aliphatic polyamide A and aromatic polyamide B, and the mass ratio of aliphatic polyamide A and aromatic polyamide B is 95 / 5-60 / 40. The polyamide resin in the present embodiment is not particularly limited as long as it satisfies such a configuration and satisfies the arc resistance, heat resistance, transparency, and molding fluidity necessary for the fuse housing.
As a preferable aspect of the polyamide resin in the present embodiment, there is at least one melting point and at least one solidification temperature, at least one melting point Tm is 255 ° C. ≧ Tm ≧ 200 ° C., and at least one The two solidification temperatures Tc are 220 ° C. ≧ Tc ≧ 170 ° C. The at least one melting point Tm is more preferably 250 ° C. ≧ Tm ≧ 210 ° C., and further preferably 245 ° C. ≧ Tm ≧ 220 ° C. The at least one solidification temperature Tc is more preferably 210 ° C. ≧ Tc ≧ 180 ° C., and further preferably 205 ° C. ≧ Tc ≧ 185 ° C. When such a polyamide resin is included, the fuse housing of the present embodiment tends to be able to ensure better molding fluidity and to further improve the productivity by taking a large number of different types.
Further, it also includes a polyamide resin having a melting point of 200 ° C. or higher, and at least one of the polyamide resins having a melting point of 200 ° C. or higher is a copolymer and / or a mixture of aliphatic polyamide A and aromatic polyamide B. preferable. When a polyamide resin having a melting point of 200 ° C. or more is used, there is a tendency that melting, deformation, and the like due to heat generation at the time of melting the fuse fusible body can be more effectively prevented.
The melting point Tm and the solidification temperature Tc can be measured by DSC (Differential Scanning Calorimetry) according to Japanese Industrial Standard (JIS) K-7121 as follows. First, after holding the measurement sample at 300 ° C. for 3 minutes, the measurement sample is lowered to 100 ° C. at a temperature decrease rate of 20 ° C./min. The solidification peak top temperature at this time can be obtained as the solidification temperature Tc. Furthermore, after maintaining at 100 ° C. for 3 minutes, the melting peak top temperature that appears when the temperature is raised to 300 ° C. at a rate of temperature increase of 20 ° C./min can be determined as the melting point.

  Specific examples of the aliphatic polyamide A include, but are not limited to, polyamide 66, polyamide 6, polyamide 610, polyamide 612, polyamide 11, polyamide 12, and the like. These can be used alone or in combination of two or more. Preferably, one or more kinds are selected from polyamide 66, polyamide 6, polyamide 610, polyamide 612, polyamide 12, and polyamide 11, and more preferably one or more kinds are selected from polyamide 66 and polyamide 6. In the present embodiment, it is particularly preferable that the aliphatic polyamide A includes the polyamide 66 from the viewpoint of heat resistance, molding productivity, and arc resistance. In addition, these can use a commercial item and can also synthesize | combine and use it by various well-known methods.

  Specific examples of the aromatic polyamide B include, but are not limited to, for example, polyamide 6T obtained by polymerizing hexamethylenediamine and terephthalic acid, polyamide 6I obtained by polymerizing hexamethylenediamine and isophthalic acid, and metaxylylene diene. Examples thereof include polyamide MXD6 obtained by polymerizing amine and adipic acid, and polyamide 9T obtained by polymerizing nonanediamine and terephthalic acid. These can be used alone or in combination of two or more. Preferably, at least one selected from polyamide 6I and polyamide 6T is used, and polyamide 6I is more preferable. That is, in the present embodiment, it is particularly preferable that the aromatic polyamide B includes the polyamide 6I from the viewpoint of transparency and molding productivity. In addition, these can use a commercial item and can also synthesize | combine and use it by various well-known methods.

The mass ratio (A / B) of the aliphatic polyamide A and the aromatic polyamide B in the copolymer and / or mixture of the aliphatic polyamide A and the aromatic polyamide B is 95/5 to 60/40. In the case where the above range is satisfied, the desired fuse housing of this embodiment having excellent transparency, heat resistance and fluidity can be obtained. From the same viewpoint, it is preferably 90/10 to 70/30, more preferably 90/10 to 65/35, and still more preferably 85/15 to 70/30. In addition, the said mass ratio (A / B) can be calculated | required by < ¹ > H-NMR measurement.

  The copolymer of the aliphatic polyamide A and the aromatic polyamide B is not limited to the following, but is preferably 66 / 6I, 66/6 / 6I, 66 / 6I / 6T, 66/6 / 6I / 6T. 6 / 6T, 6 / 6I / 6T, 66 / 9T, 66/6 / 9T, 66 / MXD6, 6 / MXD6, 66/6 / MXD6, and more preferable embodiments include 66 / 6I and 66. / 6 / 6I, 66 / 6I / 6T, and 66/6 / 6I / 6T. These can be used alone or in combination of two or more.

(Inorganic filler)
The fuse housing of the present embodiment can further include an inorganic filler. Here, in this embodiment, from the viewpoint of further improving the heat resistance, it is preferable to further include 1 to 30 parts by mass of an inorganic filler with respect to 100 parts by mass of the polyamide resin described above, and more preferably 2 to 2 parts. 20 parts by mass, more preferably 5 to 10 parts by mass. When content of the said inorganic filler shall be 30 mass parts or less, it exists in the tendency which can ensure transparency and fluidity | liquidity more favorably.

Examples of the inorganic filler include, but are not limited to, for example, titanium oxide (TiO), dititanium trioxide (Ti ₂ O ₃ ), titanium dioxide (TiO ₂ ), glass fiber, carbon fiber, calcium silicate fiber, Potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, Aluminum hydroxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, fluorine Chemical Um, montmorillonite, swelling fluorine mica, and apatite, and the like. These can be used alone or in combination of two or more.

  In this embodiment, it is preferable that the inorganic filler includes a layered silicate dispersed at a nano level. In this case, heat resistance (high-temperature shape retention) tends to be improved efficiently, and transparency can be effectively prevented from being hindered by the blending of the inorganic filler. In addition, adding layered silicate itself contributes to more effective improvement of heat resistance. The layered silicate will be described in detail below.

  The layered silicate in the present embodiment has a structure composed of a negatively charged crystal layer (silicate layer) containing silicate as a main component and a cation having ion exchange ability interposed between the layers. The silicate layer is a basic unit constituting the layered silicate, and is a plate-like inorganic crystal obtained by breaking the layer structure of the layered silicate (hereinafter referred to as “cleavage”). The silicate layer in this embodiment means the lamination state of this layer one by one or an average of 5 layers or less. Here, “dispersed at the nano level” means that when the silicate layer of the layered silicate is dispersed in the polyamide resin matrix, each layer maintains an average interlayer distance of 2 nm or more and does not form a lump. The state which is doing. Here, the interlayer distance is the distance between the centers of gravity of the silicate layers. Such a state can be confirmed by, for example, observing a transmission electron micrograph of the obtained layered silicate-containing polyamide resin test piece.

  The layered silicate can be used regardless of whether it is a natural product or an artificial product. For example, the layered silicate is not limited to the following. (Fluorine mica, muscovite, paragonite, phlogopite, lepidrite, etc.), brittle mica family (margarite, clintonite, anandite, etc.), chlorite group (donbasite, sudite, kukeite, clinochlore, chamosite, nimitite, etc.), etc. Is mentioned. In the present embodiment, Na-type or Li-type swellable fluorinated mica or montmorillonite is preferably used. In particular, swellable fluorinated mica is excellent in whiteness, and thus is preferable in terms of the appearance of the obtained resin composition.

Swellable fluorine mica generally has a structural formula represented by the following formula, and can be obtained by a melting method or an intercalation method.
Na _α (Mg _x Li _β ) Si ₄ O _y F _z
(Where 0 ≦ α ≦ 1, 0 ≦ β ≦ 0.5, 2.5 ≦ x ≦ 3, 10 ≦ y ≦ 11, 1.0 ≦ z ≦ 2.0)

Montmorillonite is generally represented by the following formula, and can be obtained by purifying a naturally occurring product using water treatment or the like.
M _a Si ₄ (Al _2-a Mg) O ₁₀ (OH) ₂ .nH ₂ O
(In the formula, M represents a cation such as sodium, and 0.25 ≦ a ≦ 0.6. Further, the number of water molecules bonded to the ion-exchangeable cation between layers depends on conditions such as cation species and humidity. (It is represented by nH ₂ O in the formula.)

  In addition, montmorillonite is known to have the same type of ion substitution product such as magnesia montmorillonite, iron montmorillonite, iron magnesia montmorillonite, and these may be used.

  In the present embodiment, it is preferable that the inorganic filler contains apatite and is dispersed so that 30% or more of the particle interface of the apatite is in contact with the polyamide resin. In this case, heat resistance (high-temperature shape retention) tends to be improved efficiently, and transparency can be effectively prevented from being hindered by the blending of the inorganic filler. In addition, adding apatite itself contributes to transparency and discoloration resistance (maintenance of transparency) depending on the use environment. The apatite will be described in detail below.

A typical composition of the apatite in the present embodiment is not limited to the following, but examples thereof include Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ (hydroxyapatite), Ca ₁₀ (PO ₄ ) ₆ F ₂ (fluorapatite). ), Ca ₁₀ (PO ₄ ) ₆ Cl ₂ (chlorine apatite), and their carbonic acid-containing materials, etc., but may not strictly match these chemical compositions. Among the above, hydroxyapatite is preferable from the viewpoint of economy and the like.

Among the apatites, the raw material for hydroxyapatite is not limited to the following, but an apatite raw material that can form apatite under the polymerization conditions of the polyamide resin, such as calcium monohydrogen phosphate (CaHPO ₄ ), calcium monohydrogen phosphate. Dihydrate (CaHPO ₄ · 2H ₂ O), calcium dihydrogen phosphate (CaH ₂ P ₂ O ₇ ), calcium dihydrogen phosphate monohydrate (Ca (H ₂ PO ₄ ) ₂ · H ₂ O ), Calcium diphosphate (α- and β-Ca ₂ P ₂ O ₇ ), tricalcium phosphate (α- and β-Ca ₃ (PO ₄ ) ₂ ), tetracalcium phosphate (Ca ₄ (PO ₄ ) ₂ O) ), Octacalcium phosphate pentahydrate (Ca ₈ H ₂ (PO ₄ ) ₆ .5H ₂ O), calcium phosphite monohydrate (CaHPO ₃ .H ₂ O), and the like.

  As raw materials for fluorapatite, chlorapatite, and carbonate-containing apatite, compounds containing fluorine ions, chlorine ions, and carbonate ions are added to the raw materials. These raw materials may be used alone or in combination of two or more.

Among these apatite raw materials, calcium monohydrogen phosphate and its dihydrate are most preferable from the viewpoint of cost and ease of handling. As can be seen from the phase diagram of the CaO—H ₂ O—P ₂ O ₅ system shown by Van Wazer in Phosphorus and it's Compounds, 1 (1958), the synthesis of calcium monohydrogen phosphate is carried out in the presence of water. It can be obtained by mixing an acid compound and a calcium compound. For example, a method in which an alkali phosphate solution and a calcium chloride solution are dropped into a potassium dihydrogen phosphate solution and reacted at about 100 ° C., a method in which calcium carbonate or calcium hydroxide and a phosphoric acid aqueous solution are mixed, and the like can be exemplified. .

  A preferable dispersion state of the apatite is a state where the particle interface is in contact with the polyamide resin for 30% or more as described above, and more preferably a state where it is in contact with 50% or more. When the proportion of the apatite particle interface in contact with the polyamide resin is 30% or more, sufficiently good toughness tends to be secured. The interface observation of the apatite particles is performed using, for example, SEM (scanning electron microscope) -EDX (energy dispersive X-ray spectrum) after cooling the molded product (fuse housing) with liquid nitrogen or the like, etching and coating treatment. Can do.

As a specific evaluation method, first, the presence state of P (phosphorus) and Ca (calcium) is measured by EDX analysis to confirm the position of the apatite particles. Next, at least 10 particles are arbitrarily selected from the apatite particles, and an electron beam is fixed to the substantially central portion, and EDX is measured. Average peak intensities I _C , I _P , and I _Ca of C (carbon) derived from polyamide resin obtained by EDX measurement and P (phosphorus) and Ca (calcium) derived from apatite are calculated and calculated by the following formulas. can do.
Ratio of interface of apatite particles in contact with polyamide resin (%) = I _C / (I _C + I _P + I _Ca ) × 100

  In this embodiment, it is preferable that an inorganic filler contains a glass filler (glass fiber). In this case, it exists in the tendency which can give favorable intensity | strength by house fusing. The said glass filler is demonstrated in detail below. The glass fiber is not particularly limited as long as it is a glass fiber usually used as a reinforcing material. For example, chopped strands that have been cut in advance to a length of 0.5 to 6 mm, middle fibers that have been crushed in advance and have a prescribed fiber length distribution, cut fibers, and the like can be used. Moreover, the glass fiber surface-treated with the sizing agent or the coupling agent can be used if necessary.

(Other additives)
In this embodiment, as long as the characteristics of the fuse housing are not significantly impaired, other heat stabilizers, antioxidants, reinforcing materials, dyes, pigments, anti-coloring agents, weathering agents, flame retardants, plasticizers, crystals A nucleating agent, a release agent and the like may be added, and these may be added as necessary when producing the polyamide resin to be used or mixing the polyamide resin. Examples of other reinforcing materials include clay, talc, calcium carbonate, zinc carbonate, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zeolite, hydro Examples include talcite, boron nitride, and graphite.

  Examples of the antioxidant include an inorganic antioxidant and an organic antioxidant. Examples of the inorganic antioxidant include, but are not limited to, copper iodide, copper acetate, potassium iodide, bromide, and the like. Examples thereof include copper, potassium bromide, iron oxide and the like. These can be used alone or in combination of two or more. Examples of organic antioxidants include, but are not limited to, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like. The said antioxidant may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, as said mold release agent, although not limited to the following, a metal soap type | system | group lubricant etc. can be mentioned, for example.

(Fuse housing manufacturing method)
Although the fuse housing of this embodiment is not limited to the following, it can be manufactured by normal molding methods, such as injection molding, for example.

  Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.

  First, evaluation methods for various properties of polyamide resin compositions or fuse housings in Examples and Comparative Examples are shown below.

[Melting point Tm, solidification temperature Tc]
The polyamide resin of each example was subjected to DSC measurement as follows. That is, in accordance with Japanese Industrial Standard (JIS) K-7121, the solidification peak top temperature (Tc) that appears when the temperature is lowered to 100 ° C. at a temperature lowering rate of 20 ° C./min after being held at 300 ° C. for 3 minutes by DSC. Obtained. Further, after being held at 100 ° C. for 3 minutes, a melting peak top temperature (Tm) that appears when the temperature was raised to 300 ° C. at a temperature rising rate of 20 ° C./min was obtained. A DSC8500 manufactured by PerkinElmer was used as a measuring device.

[Parallel light transmittance]
Using a SE50 molding machine manufactured by Sumitomo Heavy Industries, Ltd., the polyamide resin composition of each example was molded into a flat plate (60 × 60 × 1 mmt) under conditions of a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C. Based on JISK 7105, the parallel light transmittance was measured using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. In addition, the obtained numerical value can also be evaluated based on the following criteria.
○: 80% or more Δ: 70 to less than 80% ×: less than 70%

[High temperature shape retention]
The temperature of the heat rod for glow wire test was set to 600 ° C., and the flat plate after being left for 90 seconds after being brought close to 3 mm to the flat plate (60 × 60 × 1 mmt) formed at the time of measuring the parallel light transmittance as described above. The state was confirmed visually. That is, the high temperature shape retention was evaluated based on the following criteria.
◎: Almost no change ○: No significant change in appearance due to cloudiness x: Large change in appearance due to perforation or melting

[Liquidity]
Using SE130 manufactured by Sumitomo Heavy Industries, Ltd. as a molding machine, the polyamide resin composition of each example was applied to a spiral flow mold (width 10 mm × thickness 1 mm) under a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C. with an injection pressure of 100 MPa. Was injection molded. The flow length from the gate to the flow end of the obtained molded product was measured. That is, fluidity was evaluated based on the following criteria.
◎: 300 mm or more ○: 200 to less than 300 mm Δ: 100 to less than 200 mm ×: less than 100 mm

[Arc resistance]
The surface of the flat plate (60 × 60 × 1 mmt) obtained for the parallel light transmittance measurement described above was wiped with ethanol, and the state was adjusted for 48 to 72 Hr in an environment of 23 ° C. and 50% RH. Using this flat plate, arc resistance was measured with an arc resistance tester TSC-31 manufactured by Tokyo Seiden Co., Ltd. according to ASTM-D495. That is, arc resistance was evaluated based on the following criteria.
◎: 130 s or more ○: 110 to less than 130 s Δ: 90 to less than 110 s ×: less than 90 s

Example 1
4.0 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.7 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.2 kg of adipic acid and 5.0 kg of pure water were charged into an autoclave and sufficiently stirred. Thereafter, the atmosphere was replaced with nitrogen, and the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground. The obtained pulverized polymer was put in an evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The ratio of the polyamide 66 / 6I copolymer obtained by solid phase polymerization was 85/15.

(Example 2)
A polyamide 66 / 6I copolymer was obtained by the same production method as in Example 1 except that the equimolar salt of isophthalic acid and hexamethylenediamine was changed to 1.4 kg. The obtained polyamide 66 / 6I copolymer had a ratio of 75/25.

(Example 3)
A polyamide 66 / 6I copolymer was obtained by the same production method as in Example 1 except that the equimolar salt of isophthalic acid and hexamethylenediamine was changed to 1.2 kg. The polyamide 66 / 6I copolymer thus obtained had a ratio of 70/20. Further, 90 parts by mass of this 66 / 6I copolymer and 10 parts by mass of polyamide 6 [trade name 1013B: manufactured by Ube Industries, Ltd.] were previously mixed with a tumbler mixer, and a TEM35φ twin-screw extruder manufactured by Toshiba Machine Co., Ltd. The melt-kneaded product extruded at (setting 280 ° C., screw rotation speed 300 rpm) was cooled with water in a strand form and pelletized to obtain the resin composition of Example 3.

Example 4
4.0 kg equimolar salt of adipic acid and hexamethylenediamine, 1.8 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.3 kg of equimolar salt of terephthalic acid and hexamethylenediamine, 0.2 kg of adipic acid, pure water 5.0 kg was charged into an autoclave and sufficiently stirred. Thereafter, the temperature was raised from room temperature to 220 ° C. with stirring for about 1 hour while purging with nitrogen. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground. The obtained pulverized polymer was put in an evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The ratio of the polyamide 66 / 6I / 6T copolymer obtained by solid phase polymerization was 65/30/5.

(Example 5)
4.0 kg equimolar salt of adipic acid and hexamethylenediamine, 2.0 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.7 kg of equimolar salt of terephthalic acid and hexamethylenediamine, 0.2 kg of adipic acid, pure water 5.0 kg was charged into an autoclave and sufficiently stirred. Thereafter, the temperature was raised from room temperature to 220 ° C. with stirring for about 1 hour while purging with nitrogen. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground. The obtained pulverized polymer was put in an evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The ratio of the polyamide 66 / 6I / 6T copolymer obtained by solid phase polymerization was 60/30/10.

(Example 6)
4.0 kg equimolar salt of adipic acid and hexamethylenediamine, 1.4 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.7 kg of equimolar salt of terephthalic acid and hexamethylenediamine, 0.2 kg of adipic acid, pure water 5.0 kg was charged into an autoclave and sufficiently stirred. Thereafter, the temperature was raised from room temperature to 220 ° C. with stirring for about 1 hour while purging with nitrogen. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground. The obtained pulverized polymer was put in an evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The ratio of the polyamide 66 / 6I / 6T copolymer obtained by solid phase polymerization was 60/20/10. Furthermore, 90 parts by mass of this 66 / 6I / 6T copolymer and 10 parts by mass of polyamide 6 [trade name 1013B: manufactured by Ube Industries, Ltd.] were mixed in advance with a tumbler mixer, and TEM35φ biaxial manufactured by Toshiba Machine Co., Ltd. The melt-kneaded product extruded by an extruder (setting: 280 ° C., screw rotation speed: 300 rpm) was cooled in a strand form with water and pelletized to obtain a resin composition of Example 6.

(Examples 7 to 9)
100 parts by mass of the polyamide 66 / 6I copolymer obtained in Example 2 and 2 parts by mass, 5 parts by mass, 10% of GF [trade name CS03JA416 (average fiber diameter: 10 μm): manufactured by Asahi Fiber Glass Co., Ltd.] The melted and kneaded material blended with parts by mass and extruded with a TEM35φ twin screw extruder (setting: 280 ° C., screw rotation speed: 300 rpm) manufactured by Toshiba Machine Co., Ltd. was cooled with water in a strand form and pelletized to obtain Examples 7 and 8, respectively. 9 resin compositions were obtained.

(Comparative Example 1)
A polyamide 66 / 6I copolymer was obtained by the same production method as in Example 1 except that the equimolar salt of isophthalic acid and hexamethylenediamine was changed to 0.2 kg. The obtained polyamide 66 / 6I copolymer had a ratio of 97/3.

(Comparative Example 2)
A polyamide 66 / 6I copolymer was obtained by the same production method as in Example 1 except that the equimolar salt of isophthalic acid and hexamethylenediamine was changed to 4.0 kg. The obtained polyamide 66 / 6I copolymer had a ratio of 50/50.

(Comparative Example 3)
4.0 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.2 kg of adipic acid and 5.0 kg of pure water were charged into an autoclave and sufficiently stirred. Thereafter, the temperature was raised from room temperature to 220 ° C. with stirring for about 1 hour while purging with nitrogen. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground.

(Comparative Example 4)
4.0 kg of equimolar salt of adipic acid and hexamethylenediamine, 1.0 kg of ε-caprolactam, 0.2 kg of adipic acid and 5.0 kg of pure water were charged into an autoclave and sufficiently stirred. Thereafter, the temperature was raised from room temperature to 220 ° C. with stirring for about 1 hour while purging with nitrogen. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground. The obtained pulverized polymer was put in an evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The ratio of the polyamide 66/6 copolymer obtained by solid phase polymerization was 80/20.

(Comparative Example 5)
80 parts by mass of polyamide 66 obtained in Comparative Example 3 and 20 parts by mass of polyamide 6 [trade name 1013B: manufactured by Ube Industries, Ltd.] were mixed in advance using a tumbler mixer, and TEM35φ biaxial manufactured by Toshiba Machine Co., Ltd. The melt-kneaded product extruded by an extruder (setting 280 ° C., screw rotation speed 300 rpm) was water-cooled in a strand form and pelletized to obtain a resin composition of Comparative Example 5.

Table 1 shows the results of evaluating the respective physical properties of the polyamide resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5 and molded articles molded from the polyamide resin compositions as described above. In Table 1, the numerical value corresponding to each polyamide indicates the number of parts by mass. In addition, as described above, PA6 (trade name 1013B, manufactured by Ube Industries, Ltd.), PA66 (trade name 1402S, manufactured by Asahi Kasei Chemicals Corporation), PA6I, and PA6T are used as examples. Table 2 shows the results of physical property evaluation.
PA6I and PA6T were obtained as follows. 4 kg of equimolar salt of isophthalic acid and hexamethylenediamine and 5.0 kg of pure water were charged into an autoclave and sufficiently stirred. Thereafter, the temperature was raised from room temperature to 160 ° C. with stirring for about 1 hour while purging with nitrogen. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 200 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground. The obtained pulverized polymer was put in an evaporator and subjected to solid phase polymerization at 180 ° C. for 10 hours under a nitrogen stream to obtain polyamide 6I.
4 kg of equimolar salts of terephthalic acid and hexamethylenediamine and 5.0 kg of pure water were charged into an autoclave and sufficiently stirred. Thereafter, the temperature was raised from room temperature to 250 ° C. with stirring for about 1 hour while purging with nitrogen. At this time, although the internal pressure was 1.76 MPa-G due to the natural pressure of water vapor in the autoclave, the heating was further continued while removing water from the reaction system so that the pressure was not higher than 1.76 MPa-G. After 2 hours, when the internal temperature reached 300 ° C., the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 4 kg of polymer was taken out and ground. The obtained pulverized polymer was put into an evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream to obtain polyamide 6T.

  As can be seen from Tables 1 and 2, the type or amount of polyamide used affects the physical properties of the polyamide resin composition and its molded product. That is, by containing the aliphatic polyamide and the aromatic polyamide in a desired ratio in this embodiment, while ensuring sufficient arc resistance, excellent heat resistance and transparency are exhibited, and further, the raw material is good. It can be seen that a fuse housing having excellent productivity due to fluidity can be obtained. In addition, by determining the blending in consideration of each physical property of polyamide shown in Table 2, the three items of parallel light transmittance (transparency), high temperature shape retention (heat resistance), fluidity (molding productivity). The physical property balance can be made particularly good. As can be seen from Table 2, it is particularly preferable to select PA66 and PA6I as the combination of polyamides.

Claims (8)

A fuse housing that covers a pair of metal terminals connected by a fusible body and has an insulating property,
Including polyamide resin,
The polyamide resin is a copolymer and / or a mixture of an aliphatic polyamide A and an aromatic polyamide B;
The fuse housing whose mass ratio (A / B) of the said aliphatic polyamide A and the said aromatic polyamide B is 95 / 5-60 / 40.   The fuse housing of claim 1, wherein the aromatic polyamide comprises polyamide 6I.   The fuse housing of claim 1 or 2, wherein the aliphatic polyamide comprises polyamide 66.   The polyamide resin has at least one melting point and at least one solidification temperature, at least one melting point Tm is 255 ° C. ≧ Tm ≧ 200 ° C., and at least one solidification temperature Tc is 220 ° C. 4. The fuse housing according to claim 1, wherein ≧ Tc ≧ 170 ° C. 5.   The fuse housing according to any one of claims 1 to 4, further comprising 1 to 30 parts by mass of an inorganic filler with respect to 100 parts by mass of the polyamide resin.   The fuse housing of claim 5, wherein the inorganic filler comprises a layered silicate dispersed at a nano level.   The fuse housing according to claim 5 or 6, wherein the inorganic filler contains apatite and is dispersed so that 30% or more of the particle interface of the apatite is in contact with the polyamide resin.   The fuse housing according to claim 5, wherein the inorganic filler includes a glass filler.