JPH01100802A - Ultraviolet setting type insulation cable - Google Patents

Abstract

PURPOSE:To improve moldability and prevent thermal brittlement by blending the predetermined quantity of polyester resin, epoxy resin and Lewis acid freeing type photochemical polymerization intitiator respectively with polyethylene terephthalate resin(PET). CONSTITUTION:A mixture of one, or two ore more types of cationic polymerization compounds mainly comprised of polyethylene terephthalate resin containing PET as a main component and epoxy resin containing two or more oxylan rings, is blended with polyethylene terephthalate resin by 30wt.% or less, and further with a cationic polymerization compound freeing a Lewis acid catalyst via ultraviolet irradiation containing 0.1 to 10wt.% of a photochemical polymerization initiator for the compound. This blended material is an electric insulation material of good moldability and free from thermal brittlement at a relatively low temperature of approximately 150 deg.C via only ultraviolet irradiation.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is an ultraviolet ray film that improves the phenomenon in which polyethylene terephthalate resin-coated insulated wires that are not subjected to cooling stretching treatment become brittle when heated at a relatively low temperature, for example, 150°C for several hours. The present invention relates to an insulated wire coated with a curable resin composition.

[Conventional technology]

Polyethylene terephthalate resin (hereinafter referred to as PET)
is used in large quantities mainly in the form of fibers and films for electrical insulation and textile industries. It is well known that the crystal structure of all these materials is oriented and regulated by cooling stretching treatment and heat setting treatment, making them strong and flexible, and that the crystal structure does not change easily at temperatures of around 200°C and retains its flexibility. That's right.

[Problem that the invention seeks to solve]

However, when this PET is extruded and coated on an electrical conductor, it is impossible to perform a subsequent cooling and stretching process, and as a result, the PET
T-covered insulated wires suffer from severe thermal embrittlement and cannot be put to practical use.

In view of these points, the inventors of the present invention coated a conductor with this useful PET, which has been used for many years, to obtain a PET-based insulated wire that does not become thermally embrittled even without a subsequent cooling and stretching process. succeeded in.

PET molded products are highly flexible even without cooling stretching treatment by adjusting the cooling rate, etc., but even at 150°C, which is relatively low compared to the processing temperature, the crystal structure changes in a few hours. become brittle. Therefore, in order to prevent changes in the crystal structure, we considered mixing various functional resins and performing crosslinking with various crosslinking agents, but the crosslinking progressed partially or completely depending on the PET molding temperature. The molded product itself could not be stably obtained due to gelation.

However, the present inventors have developed a method using certain functional resins.

Only compositions containing a Lewis acid-free photopolymerization initiator capable of initiating polymerization of this functional resin are stable to heat, and due to the plasticizing effect of the low melting point polyester resin and epoxy resin blended with PET, Finally, it was discovered that the extrusion temperature was lowered, and at that temperature it hardly decomposed and could not only be freely molded but also retain its post-ultraviolet polymerization function.

In this way, by mixing an epoxy resin with a composition containing PET and a polyester resin that helps plasticize it, and adding a Lewis acid free type photopolymerization initiator, it is possible to freely mold it, and only needs to be treated with ultraviolet light afterward. We succeeded in obtaining an innovative PET-based insulated wire that does not cause thermal embrittlement.

[Means for solving problems]

The ultraviolet curable insulated wire of the present invention comprises one or more of a PET resin whose main component is PET and a cationic polymerizable compound whose main component is an epoxy resin having two or more oxirane rings in each molecule. The amount of the mixture is 30% by weight or less based on the PET resin.

Further, an electric conductor is coated with an ultraviolet curable resin composition containing 0.1 to 10% by weight of the cationic polymerizable compound, based on the cationic polymerizable compound, of a photopolymerization initiator that releases a Lewis acid catalyst upon irradiation with ultraviolet rays; This is a completely curved electric wire that has been hardened by ultraviolet irradiation.

The PET resin used in the present invention is preferably a commercially available grade for films or fibers, or a grade for bottles with an increased degree of polymerization by solid phase polymerization, but the softening point is 1.
If the temperature is 70° C. or higher, a material containing an isophthalic acid component or a polybutylene terephthalate resin can also be used.

In addition, in order to improve the processability of PET at low temperatures, polyester resins such as Erytail (manufactured by Unitika Co., Ltd., trade name) or low molecular weight polyester resins such as Desmorphene (manufactured by Bayer AG, trade name) are used. Preferably, the species or a mixture of two or more species is substituted in an amount of 70% by weight or less of the PUT.

The cationically polymerizable compound used in the present invention is one or more cationically polymerizable compounds whose main component is an epoxy resin having two or more oxirane rings in one molecule, and this epoxy resin includes bisphenol A type epoxy resin. ,
Novolac type epoxy resins are preferred.

Examples of such bisphenol A epoxy resin include Epicoat 828. Epicote 834, Epicote 836, Epicote 1001 (all manufactured by Shell Chemical Co., Ltd.,
Product name), DER331, DER332, DER661
(that's all.

Manufactured by Dow Chemical Company, trade name), Araldite 260, Araldite 280. Examples include Araldite 6071 (trade name, manufactured by Ciba Geigy), which may be used alone or in combination.

Further, as the novolac type epoxy resin, for example, Epicoat 152. Epicote 154 (and above).

Manufactured by Shell Chemical Co., Ltd., trade name), Araldite EPN113
8. Araldite EPN1139, Araldite ECN
1235, Araldite ECN1273. Araldite ECN1280, Araldite ECN1299 (and above,
Manufactured by Ciba Geigy, product name), DEN431, DEN4
38 (trade name, manufactured by The Dow Chemical Company), and these may be used alone or in combination.

A monofunctional epoxy diluent may be used in the cationic polymerizable compound within a range that does not deteriorate the curing properties. Examples of such monofunctional epoxy diluents include phenyl glycidyl ether and t-butyl glycidyl ether.

Furthermore, it is also possible to use a cationically polymerizable vinyl compound mixed with the epoxy resin, and examples of such cationically polymerizable vinyl compound include styrene, allylbenzene, triallyl isocyanate, triallylcyanate, vinyl ether, and N-vinyl carbazole,
Examples include N-vinylpyrrolidone.

As the photopolymerization initiator used in the present invention, which releases a Lewis acid catalyst that initiates polymerization of a cationic polymerizable compound by ultraviolet irradiation, photosensitive aromatic onium salts of Group VIa elements or Group Va elements, etc. can give.

The photosensitive aromatic onium salt of Group VIa element or Group Va element has the general formula (I)=((R,)a(
R2), (R3). Y)4d(MQ--""n)
[I) [In the formula, R is a monovalent aromatic organic group, R2 is a monovalent aliphatic organic group selected from the group consisting of an alkyl group, a cycloalkyl group, and a substituted alkyl group, and R3 is an aliphatic organic group and a heterocyclic group selected from aromatic organic groups or a polyvalent organic group constituting a condensed ring structure, Y is a Group VIa element of S, Se, Dye, or N, P, As, Sb and B
Group Va element selected from i, M is a metal or metalloid,
Q represents a halogen atom, a is an integer of 0 to 4, and b is 0
an integer of ~2, C is an integer of O~2, and (a +
b + c ) is equal to the valence of Y, and 3. when Y is a Group VIa element. When Y is a group Va element, it is equal to 4, a=(m-n) holds, and n is an integer from 2 to 7 and M
and m represents an integer greater than n and equal to or less than 8], and as an onium salt of a Group VIa element, for example, in the formula r, R represents an alkyl group], etc. As onium salts of group Va elements,
For example, etc. Diazonium salts and halonium salts are known as photopolymerization initiators that liberate Lewis acid catalysts, but the catalysts have poor thermal stability, and according to experiments conducted by the present inventors, it is difficult to use them in the present invention. It is.

Furthermore, from the aspect of thermal stability of the catalyst, the present invention includes VI.
Onium salts of group a elements are preferred.

The amount of the Lewis acid free photopolymerization initiator that is active against the cationically polymerizable compound is 0.1 to 10% by weight, preferably 1 to 5% by weight of the cationically polymerizable compound;
When the amount is less than 0.1% by weight, the crosslinking reaction rate due to ultraviolet rays tends to be slow and the processing time tends to be too long.
If it exceeds % by weight, the cost of the catalyst will be high and the price of the resin composition will become high.

The insulated wire of the present invention covers a conductor with the resin composition,
It is cured by ultraviolet irradiation. The above-mentioned resin composition can be coated onto a conductor using a conventional extruder, and furthermore, by using a T-die, it is also possible to produce an insulated conductor strip or foil for use in electronic circuit boards and the like.

For curing treatment by ultraviolet crosslinking after extrusion processing, irradiation with a light source such as a low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, carbon arc lamp, etc. or electron beam irradiation may be used, and the treatment may be performed in a separate process. An irradiation device is installed in the extruder, and the water cooling tank used to cool the wire after being coated with the resin composition is shortened, and the residual heat of the coated wire is used to accelerate the curing reaction, while a return wheel is used to remove the ultraviolet irradiation area. It is economical to carry out cross-linking and curing treatment continuously by passing the resin through the tube repeatedly.

[Embodiments of the invention]

Next, the insulated wire of the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example I 60 parts of PET pellets were frozen and ground, thoroughly dried, and 25 parts by weight of Desmorphen F-951 (manufactured by Bayer AG, low molecular weight polyester resin) and 15 parts by weight of Epicote 828 (bisphenol A type epoxy resin) were added. mix,
Kneaded in a kneader at 280°C for 10 minutes, then cooled.
Pelletize and dry thoroughly. 175 of these pellets were taken, freeze-pulverized again, and dried thoroughly to obtain porous pellets containing 50% by weight of triphenylsulfonium hexafluoroantimonate (photopolymerization initiator).
1.0 parts by weight of a propylene carbonate solution is thoroughly mixed at room temperature to prepare a so-called catalyst masterbatch.

This masterbatch amount is 175 and the remaining pellets are 475.
The amounts were thoroughly mixed and put into the hopper of an extruder with L/D = 20, which was maintained at a barrel temperature of 220°C and a head temperature of 240°C.

1. Thickness 4 on 0 mm diameter annealed copper wire by crosshead.
Extrusion processing was carried out at a wire speed of 0 μm and a wire speed of 50 m/min to obtain a coated electric wire.

This electric wire is uncured before being subjected to ultraviolet irradiation treatment.

Next, this uncured wire was heated with a 21W high-pressure mercury lamp (length 25
cm, manufactured by Iwasaki Electric Co., Ltd.) were installed at 20 cm intervals, and the middle part of the mercury lamp was placed 3 m/3 m parallel to the length direction of the mercury lamp.
An insulated wire that had been subjected to ultraviolet curing treatment was obtained by running the wire for several minutes. Table 1 shows the measurement results of winding flexibility, softening point, and solvent resistance according to JIS C3003.

Example 2 50 parts by weight of PET pellets were freeze-pulverized and thoroughly dried, and 15 parts by weight of Eliteil UE-3700 (manufactured by Unitika Co., Ltd., hot melt polyester resin) and 20 parts by weight of Desmorphen F-951 (low molecular weight polyester resin) were added.
The heavy-duty part and Epikote 82,815 parts by weight were mixed, kneaded in a kneader at 280°C for 10 minutes, then cooled, pelletized, and sufficiently dried. Take 175 amounts of this mixture,
The resulting porous pellets were frozen and crushed again, and uVI6970 (50% by weight propylene carbonate solution of sulfonium salt photopolymerization initiator manufactured by GE) was added to the resulting porous pellets.
1.0 parts by weight were thoroughly mixed at room temperature to prepare a catalyst masterbatch.

Next, 115 amounts of this masterbatch and 415 amounts of the remaining pellets were mixed, and in the same manner as in Example 1, 1.
An uncured coated electric wire with a diameter of 0 mm and an insulated electric wire subjected to ultraviolet curing treatment were obtained. Table 1 shows the measurement results of winding flexibility, softening point, and solvent resistance according to JIS C3003.

Example 3 45 parts by weight of PUT pellets were freeze-pulverized, thoroughly dried, and mixed with 25 parts by weight of Eliteil UE-3700 (low melting point polyester resin), 20 parts by weight of Desmorphen F-951 (low molecular weight polyester resin), and Epicote 152. (Novolac type epoxy resin) 10 parts by weight were mixed and kneaded in a kneader at 280°C for 10 minutes, then cooled, pelletized, and sufficiently dried. Take 175 parts of this mixture, freeze-pulverize it again, dry it thoroughly, and add 1.0 parts by weight of UVl6970 (a 50% propylene carbonate solution of sulfonium salt photopolymerization initiator manufactured by GE) to the obtained porous pellets. were thoroughly mixed at room temperature to create a catalyst masterbatch.

Next, 115 of this masterbatch was mixed with 415 liters of the remaining pellets, and 1 was prepared in the same manner as in Example 1.
, an uncured coated electric wire with a diameter of 0+am and an insulated electric wire subjected to ultraviolet curing treatment were obtained. The measurement results of winding flexibility, softening point and solvent resistance according to JIS C3003 were
Shown in the table.

Example 4 40 parts by weight of PET pellets were sufficiently dried and mixed with 25 parts by weight of Elytail UE-3700 (low melting point polyester resin), 20 parts by weight of Desmorphen F-951 (low molecular weight polyester resin), and the heavy bearing part of Epicoat 82815. The mixture was kneaded in a kneader at 280°C for 10 minutes, then cooled and pelletized.

The pellets are freeze-pulverized, the resulting porous pellets are sufficiently dried, and UVl6970 (photopolymerization initiator 5
1.0 parts by weight of 0% solution) were mixed at room temperature to be sufficiently homogeneous, and the same procedure as in Example 1 was carried out to obtain a solution of 1.0 mm.
An uncured coated wire with a diameter and an insulated wire subjected to ultraviolet curing treatment were obtained. Wrapping flexibility according to JIS C3003,
Table 1 shows the measurement results of softening point and solvent resistance.

Example 5 50 parts by weight of PET in Example 2 was added to polybutylene terephthalate resin 1401-XO6 (manufactured by Toshi Co., Ltd.)
50 parts by weight, and all other conditions were the same as in Example 2 to obtain an uncured coated wire with a diameter of 1.0 IIIn and an insulated wire that had been subjected to ultraviolet curing treatment. JIS C3
Table 1 shows the measurement results of winding flexibility, softening point and solvent resistance according to 003.

Example 6 Mixing barrel 1- obtained in exactly the same manner as in Example 4 was maintained at barrel 210°C and head at 235°C L/D = 2
The mixture was put into the hopper of a No. 0 extruder, and extruded and coated onto a copper strip with a thickness of 0.2 m+m and a width of 50 mm using a T-shaped die to a thickness of 40 μm to obtain a single-sided coated copper strip.

Next, this uncured coated copper strip was run between mercury lamps at 3 m/min in the same manner as in Example 1, to obtain an insulated copper strip that had been irradiated with ultraviolet rays.

Based on the bending characteristics of this copper strip at 180°C with a diameter of 3+s, a steel ball with a diameter of 1.6 mta was placed on the coated surface, a load of 1 kg was applied thereto, 100 V AC was applied between the steel ball and the copper conductor, and the temperature was constant. Table 1 shows the softening point and solvent resistance according to JIS C3003, which were measured by increasing the temperature in a bath at a rate of about 0.degree. C./min.

Comparative Example I PET pellets were put into the hopper of an extruder with L/D = 28, which was maintained at a barrel temperature of 250°C and a head temperature of 300°C.
1.0III11 on annealed copper wire with a thickness of 40μ and a wire speed of 50m/
Extrusion processing was performed to obtain an insulated wire. JIS C3
Table 1 shows the measurement results of winding flexibility, softening point and solvent resistance according to 003.

Comparative Example 2 An insulated wire with a diameter of 1.0 mm was obtained under the same conditions as Comparative Example 1 using pellets of polybutylene terephthalate resin 1401-XO6 (manufactured by Toshi Co., Ltd.). JIS C30
Table 1 shows the measurement results of winding flexibility, softening point, and solvent resistance according to No. 03.

Comparative Example 3 775 parts by weight of PE and polyarylate resin U-100 (
Unitika Co., Ltd. 11) 25! ! An insulated wire with a diameter of 0 m++ was obtained under the same conditions as Comparative Example 1 using the extrusion mixture that was uniformly kneaded and pelletized.
Table 1 shows the measurement results of winding flexibility, softening point and solvent resistance according to C3003.

Comparative Example 4 PET pellets were put into the hopper of an extruder with L/D = 28 maintained at a barrel temperature of 250°C and a head temperature of 300°C.
A copper strip having a thickness of 0.2 mm and a width of 50 mm was coated by extrusion to a thickness of 40 μm using a die to obtain a steel strip coated on one side. Characteristics measured using exactly the same method as in Example 6 are shown in Part 1.

Comparative Example 5 85 parts by weight of PET pellets were freeze-pulverized, mixed with 15 parts by weight of Epicoat 82,815 parts by weight, and mixed with 85 parts by weight of PET pellets at 280°C in a kneader.
The mixture was kneaded for 0 minutes, then cooled, pelletized, and thoroughly dried.

A 1/S amount of this mixture was taken, frozen and crushed again, and the obtained porous pellets were thoroughly dried and then UVl69
70 (photopolymerization initiator) was thoroughly mixed at room temperature to prepare a catalyst masterbatch.

The amount of this masterbatch is 115 and the remaining amount of pellets is 475.
An attempt was made to make an insulated wire with a diameter of 1.0 m+* in exactly the same manner as in Example 1 by mixing the amounts, but the barrel could not be discharged due to insufficient temperature at 220° C. and head at 240° C.

The temperature was raised sequentially, and the melt discharge started at 240°C in the barrel and 260°C in the head, but after 5 minutes, thermal decomposition of the photopolymerization initiator was observed due to the temperature, and crosslinking gelation occurred due to the released Lewis acid. occurred inside the barrel, and an insulated wire could not be obtained.

As is clear from the experimental results shown in Table 1, the insulated wire made of only PET shown in Comparative Example 1 and the single-sided coated copper strip shown in Comparative Example 4 are severely thermally embrittled and cannot be put to practical use. Also PE
As shown in Comparative Example 2, an insulated wire made of polybutylene terephthalate resin alone, which is the same type as T, is severely thermally embrittled and cannot be put to practical use6.
Attempts have been made to mix it with T-based resins, but as shown in Comparative Example 3, the thermal embrittlement is slightly improved and can withstand deterioration for 5 hours at 200°C, but embrittlement occurs after 10 hours of deterioration. The improvement is insufficient. Furthermore, as a side effect of mixing non-quality resins, the softening point decreases significantly and the solvent resistance is also poor.

Therefore, various attempts have been made to improve thermal embrittlement and at the same time prevent a decrease in softening point and deterioration of solvent resistance. Various formulations have been studied in order to crosslink and prevent changes in the crystal structure due to heat. However, as shown in Comparative Example 5, it has the role of lowering the melting temperature of PET.

When a low melting point polyester resin or a low molecular weight polyester resin was not blended, the extrusion temperature became relatively high, gelation occurred, and a molded product could not be obtained.

On the other hand, in Examples 1 to 6 of the present invention, no gelation occurred at the extrusion processing temperature, and the resulting insulated wires had a low softening point because the epoxy resin blended was not cured without UV irradiation. , thermal embrittlement occurs and the solvent resistance is poor, but by UV irradiation treatment, the softening point and solvent resistance are improved, and the embrittlement caused by thermal deterioration at 200 degrees Celsius is almost completely improved. I understand.

Furthermore, it was confirmed that the insulated wire irradiated with ultraviolet rays according to the present invention has excellent mechanical strength, electrical insulation properties, coil windability, etc., and is an extremely useful continuous wire.

〔Effect of the invention〕

According to the present invention, by mixing an epoxy resin with a composition in which PET is blended with a polyester resin that helps plasticize, and blending a Lewis acid free type photopolymerization initiator, it is possible to freely mold An excellent PET-based insulated wire that does not cause thermal embrittlement can be obtained only by ultraviolet treatment.

Claims (4)

[Claims] (1) A mixture of one or more of a polyethylene terephthalate resin whose main component is a polyethylene terephthalate resin and a cationic polymerizable compound whose main component is an epoxy resin having two or more oxirane rings in one molecule. 30 for polyethylene terephthalate resin
% by weight or less, and further contains a photopolymerization initiator for the cationic polymerizable compound that releases the Lewis acid catalyst by ultraviolet irradiation, and 0.1 to 10% by weight based on the cationic polymerizable compound. 1. An ultraviolet-curing insulated wire characterized by being coated with UV rays and curing the wire by irradiating it with ultraviolet rays. (2) Claims characterized in that the photopolymerization initiator is one type or a mixture of two or more types selected from the group consisting of photosensitive aromatic onium salts of Group VIa elements or Group Va elements. The ultraviolet curable insulated wire according to item 1. (3) 70% by weight of polyethylene terephthalate resin
Claim 1 or Claim 1 characterized in that the following is replaced with one or a mixture of two or more selected from the group consisting of polyester resins that soften at relatively low temperatures and low molecular weight polyester resins: The ultraviolet curable insulated wire according to item 2. (4) The ultraviolet curable insulated wire according to any one of claims 1 to 3, characterized in that polybutylene terephthalate resin is used instead of polyethylene terephthalate resin.