JPH06248236A - Resin composition for coating metal wire - Google Patents

Abstract

PURPOSE:To provide a resin composition comprising two kinds of polyethersulfones having specific structures, respectively, useful for the production of high quality metal wires due to excellent surface hardness and heat resistance and capable of being applied to a wide range of wires. CONSTITUTION:The composition comprises (A)70-30wt.% of a nitrile-containing polyethersulfone of formula I or II (n is 50-150) and (B) 30-70wt.% of a polyethersulfone having at least 50mol.% of units of formula III and the remaining amount of units selected from units of formulas IV, V, etc., and having a reduced iscosity of 0.35-0.6dl/g measured in a concentration of 1g/dl in DMF at 30 deg.C. The component A is produced e.g. by copolymerizing dihydroxydiphenyl sulfone with 2,6-dichlorobenzonitrile. The component B is produced e.g. by copolymerizing 4-chloro-4'-(p-hydroxyphenyl)diphenyl sulfone with 4,4'''-dihydroxy-p-quaterphenyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coating a metal wire which forms a protective coating material such as a coil winding and has excellent surface hardness and improved heat resistance.

[0002]

2. Description of the Related Art A method for manufacturing a coil winding (so-called enamel wire) insulated by extrusion coating of a thermoplastic resin is
It has already been disclosed in European Patent Application No. 17062. This method has the drawbacks that the surface hardness and the wear resistance of the coil winding obtained from amorphous polyether sulfone are lowered. Therefore, the obtained coil winding is not suitable for the coil (or the lead wire) of the electric motor.

In order to solve such a problem, JP-A-59-42706 discloses a method of coating a metal wire with polyether sulfone having a nitrile group. However, this coil coated with polyethersulfone has not been able to sufficiently satisfy the heat resistance required for the insulated wire from the viewpoints of downsizing and weight reduction and improvement of reliability in recent electric devices.

[0004]

As described above, the resin composition such as polyether sulfone used for coating the conventional metal wire has insufficient surface hardness and / or heat resistance. The range of use was also limited.

The present invention is intended to solve the above problems, and an object of the present invention is to provide a resin composition for coating a metal wire material which has excellent surface hardness and heat resistance.

[0006]

A resin composition for coating a metal wire according to the present invention is represented by the following formulas (I) and (II):
It contains at least one kind (A) of polyether sulfone having a nitrile group in the molecule in a proportion of 70 to 30% by weight, contains at least 50 mol% of a repeating unit represented by the following formula (III), and the balance: Formulas (IV) to (XIX) below
Is at least one selected from the group consisting of repeating units represented by the following formula, and the reduced viscosity measured in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C.
The polyether sulfone (B), which is 0.35 dl / g or more and 0.6 dl / g or less, is contained in a proportion of 30 to 70% by weight, whereby the above object is achieved.

[0007]

[Chemical 4]

(In the formula, n represents an integer of 50 to 150).

[0009]

[Chemical 5]

[0010]

[Chemical 6]

The present invention will be described in detail below.

The metal wire rod coating resin composition of the present invention comprises a polyether sulfone (A) and a polyether sulfone (B) having a specific structure.

The polyether sulfone (A) is a polyether sulfone represented by the above formula (I) having a nitrile group in the molecule and / or a polyether sulfone represented by the above formula (II) having a nitrile group in the molecule. It is ether sulfone. Polyethersulfone (I) is obtained, for example, by copolymerizing dihydroxydiphenylsulfone and 2,6-dichlorobenzonitrile, and polyethersulfone (II) is obtained, for example, by dihydroxydiphenylsulfone and 2,4-dichlorobenzonitrile. It is obtained by copolymerizing and.

The method for producing the polyether sulfone (A), that is, the polyether sulfone (I) and / or the polyether sulfone (II) is not particularly limited, but is preferably polar in the presence of an alkali metal salt. A nucleophilic substitution polycondensation method of polymerizing in a solvent is used.

The alkali metal salt is preferably sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate or the like, and particularly preferably sodium carbonate or potassium carbonate. As the polar solvent, sulfolane-based solvents such as sulfolane, diphenyl sulfone and dimethyl sulfoxide, or amide-based solvents such as dimethyl acetamide and dimethyl imidazoline are preferably used. The polymerization temperature is preferably 80 to 400 ° C, more preferably 100 to 350 ° C. Furthermore, when the monomers are polymerized, the proportion of all halogen groups to all hydroxyl groups is 90 to 110 mol%.
It is preferable to carry out in the range of. In order to obtain a higher molecular weight polymer, the above ratio is preferably within the range of 95 to 105 mol%.

The polyether sulfone (B) contains a repeating unit represented by the above formula (III).

The repeating unit (III) is contained in the polyether sulfone (B) in a proportion of at least 50 mol%. When the content ratio is less than 50 mol%,
It is not preferable because it lowers the heat resistance. The polyether sulfone (B) may be composed of only the repeating unit (III), and is selected from the repeating unit (III) and the repeating units represented by the above formulas (IV) to (XIX). It may be composed of at least one kind.

When the polyether sulfone (B) is composed of only the repeating unit (III), it can be obtained, for example, by polymerizing 4-chloro-4 '-(p-hydroxyphenyl) diphenyl sulfone. When the polyether sulfone (B) is composed of the repeating unit (III) and at least one selected from the repeating units (IV) to (XIX), 4-chloro-4 ′-(p -Hydroxyphenyl) diphenyl sulfone and the corresponding repeating units (IV) to (XIX) are obtained by copolymerization. For example, when the repeating unit (IV) is contained, 4,4 ′ ″-dihydroxy-p-quaterphenyl may be used as the monomer, and when the repeating unit (XII) is contained, dihydroxydiphenylsulfone may be used as the monomer. Alternatively, dichlorodiphenyl sulfone may be used. In addition, 4,4 '''-dihydroxy-p-quaterphenyl is, for example, Journal of Chemical Society 1379-85 (194
It can be produced by the method described in 0).

The polyether sulfone (B) is contained in the resin composition of the present invention in a proportion of 30 to 70% by weight.
If the content is less than 30% by weight, the effect of improving the heat resistance is not sufficient, which is not preferable, and if the content is more than 70% by weight, the surface hardness decreases, which is not preferable.

The method for producing the polyether sulfone (B) is not particularly limited, but preferably the same method as described for the polyether sulfone (A) can be mentioned.

In order to give the above-mentioned polyether sulfone (A) and polyether sulfone (B) a specific effect, a small amount of an additive may be added in some cases. For example, a stabilizer, a fireproofing agent, or a silicone resin may be added for the purpose of improving flowability. Moreover, since a colored winding is used in practice, a pigment or a pigment such as antimony dioxide or zinc sulfide may be used in combination. Furthermore, as a filler, for example, kaolin, talc, chalk, barite, gneiss, mica, glass powder, glass spheres, chopped glass fibers, or a mixture thereof is added at a ratio of about 1 to 30% by weight. can do.

The resin composition of the present invention comprises the above-mentioned polyether sulfone (A) and polyether sulfone (B).
However, the compounding method is not particularly limited. The polyether sulfone (A) and the polyether sulfone (B) can be separately supplied to the melt-kneader, and these can be previously fed to a mortar,
It is also possible to premix using a Henschel mixer, a ball mill, a ribbon blender, etc., and then supply to the melt-kneader.

The resin composition of the present invention is used for coating a metal wire rod. This coating method is not particularly limited. For example, the resin composition may be prepared by adding dimethylformamide, N
-A method of dissolving in a polar solvent such as methylpyrrolidone and coating and baking it on a copper wire, or a method of using an extruder for producing a covered wire rod, etc. may be mentioned.

[0024]

EXAMPLES The present invention will be described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

(Examples 1 to 3 and Comparative Examples 1 and 2) Production of Polyethersulfone (A-1) First, polymerization comprising a stirrer, a gas introduction pipe, a thermometer and a condenser having a receiver at its tip. In a reaction vessel, 150.2 parts by weight of dihydroxydiphenyl sulfone, 103.2 parts by weight of 2,6-dichlorobenzonitrile were dissolved in 900 parts by weight of N-methylpyrrolidone and 300 parts by weight of chlorobenzene, and then 87.2 anhydrous potassium carbonate was added. Charge the weight part,
Nitrogen substitution was performed. Next, stirring and temperature increase were started under a nitrogen atmosphere, chlorobenzene was distilled off at 150 ° C., and then a reaction was carried out at 180 ° C. for 6 hours. Then, the polycondensation was stopped by introducing a methylene chloride stream for 30 minutes. Then, potassium chloride precipitated in the reaction solution was removed by filtration, and the filtrate was poured into a large amount of methanol to precipitate a polymer, thereby obtaining a polyether sulfone (A-1). The reduced viscosity of this polyether sulfone (A-1) is 0.6d.
It was 1 / g (23 ° C., 1% in sulfuric acid solution).

Production of Polyethersulfone (B-1) First, 4-chloro-4'- was placed in a polymerization reaction vessel equipped with a stirrer, a gas introduction tube, a thermometer and a condenser with a receiver at the tip.
(P-Hydroxyphenyl) diphenyl sulfone 100 parts by weight, anhydrous potassium carbonate 22.1 parts by weight, sulfolane 2
90 parts by weight were charged and the atmosphere was replaced with nitrogen. Next, under a nitrogen atmosphere, stirring and heating are started, and the temperature is set to 220 ° C. for 30 minutes.
The reaction was carried out at 240 ° C for 3 hours. After completion of the reaction, potassium chloride precipitated in the reaction solution was removed by filtration, and the filtrate was poured into a large amount of methanol to precipitate a polymer, thereby obtaining a polyether sulfone (B-1). The reduced viscosity of this polyether sulfone (B-1) was 0.40 dl / g (30 ° C., 1 g / dl in dimethylformamide).

Preparation of Resin Composition Polyethersulfone (A-1) obtained in the above process
And the polyether sulfone (B
-1) was dry blended in the proportions shown in Table 1 and then extruded while being melt-kneaded with a 40 mm extruder equipped with a screw to obtain a pellet-shaped resin composition in which the above polyether sulfone was uniformly blended.

The surface hardness and heat resistance of this resin composition were evaluated by the following methods. The results are shown in Table 1.

(I) Surface Hardness The resin composition was dissolved in dimethylformamide to prepare a 30% by weight solution, and a test piece was prepared according to JIS K 5400 to conduct a scratch test. (Ii) Heat-resistant resin composition Glass transition point DSC (manufactured by Seiko Denshi)
Was measured at a temperature rising rate of 20 ° C./min.

(Examples 4 to 6) In this example, as the polyether sulfone (A), the polyether sulfone (A-1) obtained in the steps of Examples 1 to 3 and Comparative Examples 1 and 2 was used. Was used.

Preparation of polyether sulfone (B-2) 100 parts by weight of 4-chloro-4 '-(p-hydroxyphenyl) diphenyl sulfone, 32.8 parts by weight of 4,4 "'-dihydroxy-p-quarterphenyl. , 4,4'-dichlorodiphenyl sulfone 27.9 parts by weight, anhydrous potassium carbonate 33 parts by weight,
Using 290 parts by weight of sulfolane, copolymerization was carried out in the same manner as in the steps of Examples 1 to 3 and Comparative Examples 1 and 2 to obtain polysulfone (B-2). The reduced viscosity of this polyether sulfone (B-2) is 0.38 dl / g.
(1 g / dl in dimethylformamide at 30 ° C).

Preparation of Resin Composition The polyether sulfone (A-1) and the polyether sulfone (B-2) obtained in the above step were used in the proportions shown in Table 1, except that the above Examples 1 to 3 and Comparative Examples 1 and 2
A resin composition was prepared in the same manner as in the step of 1. and surface hardness and heat resistance were evaluated. The results are shown in Table 1.

(Examples 7 and 8) In this example, as the polyether sulfone (A), the polyether sulfone (A-1) obtained in the steps of Examples 1 to 3 and Comparative Examples 1 and 2 was used. Was used.

Production of polyether sulfone (B-3) 100 parts by weight of 4-chloro-4 '-(p-hydroxyphenyl) diphenyl sulfone, 29.4 parts by weight of 4,4 "'-dihydroxy-p-quarterphenyl. Example 4, using 39.0 parts by weight of 4,4'-dichlorodiphenyl sulfone, 13.6 parts by weight of 4,4'-dihydroxydiphenyl sulfone, 44.1 parts by weight of anhydrous potassium carbonate and 290 parts by weight of sulfolane.
To 3 and Comparative Examples 1 and 2 were copolymerized by the same method to obtain polysulfone (B-3). The reduced viscosity of this polyether sulfone (B-3) is 0.41d.
1 / g (30 ° C, 1g / dl in dimethylformamide)
Met.

Preparation of Resin Composition The polyether sulfone (A-1) and the polyether sulfone (B-3) obtained in the above steps were used in the proportions shown in Table 1, except that the above Examples 1 to 3 and Comparative Examples 1 and 2
A resin composition was prepared in the same manner as in the step of 1. and surface hardness and heat resistance were evaluated. The results are shown in Table 1.

(Comparative Example 3) In this Comparative Example, the polyether sulfone (A) used was the polyether sulfone (A-1) obtained in the steps of Examples 1 to 3 and Comparative Examples 1 and 2 above. I was there.

Production of polyether sulfone (B-4) 4,4'-dichlorodiphenyl sulfone 100 parts by weight, 4,4'-
Using 87.2 parts by weight of dihydroxydiphenyl sulfone, 48.1 parts by weight of anhydrous potassium carbonate and 290 parts by weight of sulfolane, copolymerization was carried out in the same manner as in the steps of Examples 1 to 3 and Comparative Examples 1 and 2, Polysulfone (B
-4) was obtained. The reduced viscosity of this polyether sulfone (B-4) was 0.41 dl / g (30 ° C., 1 g / dl in dimethylformamide).

Preparation of Resin Composition The polyether sulfone (A-1) and the polyether sulfone (B-4) obtained in the above steps were used in the proportions shown in Table 1, except that the above Examples 1 to 3 and Comparative Examples 1 and 2
A resin composition was prepared in the same manner as in the step of 1. and surface hardness and heat resistance were evaluated. The results are shown in Table 1.

[0039]

[Table 1]

The mole fractions of each of the polyether sulfones (B-1) to (B-2) in Table 1 are as shown in Table 2.

[0041]

[Table 2]

[0042]

As is apparent from the above description, according to the present invention, a resin composition for coating a metal wire rod having excellent surface hardness and heat resistance can be obtained. Therefore, the resin composition of the present invention can be used for producing high-quality metal wire rods and can be applied to a wide range of wire rods.

Claims (1)

[Claims] 1. A compound represented by the following formulas (I) and (II):
It contains at least one kind (A) of polyether sulfone having a nitrile group in the molecule in a proportion of 70 to 30% by weight, and contains at least 5 repeating units represented by the following formula (III).
At least 1 selected from the group consisting of repeating units represented by the following formulas (IV) to (XIX)
Seed and in dimethylformamide at a concentration of 1 g / d
1, the reduced viscosity measured at a temperature of 30 ° C. is 0.35
A resin composition for coating a metal wire, comprising the polyether sulfone (B) in a proportion of 30 to 70% by weight, which is dl / g or more and 0.6 dl / g or less. [Chemical 1] (In the formula, n represents an integer of 50 to 150). [Chemical 2] [Chemical 3]