JPS6158103A - insulated wire - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a highly durable electric wire coated with a resin composition having a polyethylene terephthalate resin or a polybutylene terephthalate resin as a main resin that is not subjected to cooling stretching treatment, particularly at a relatively low temperature, e.g. This invention relates to an insulated wire coated with an ultraviolet curable resin composition that has improved the phenomenon of embrittlement caused by heating at 150"C for several hours.

[Prior art]

Polyethylene terephthalate resin (hereinafter referred to as PET)
is mainly i3i! )if;, in the form of films, etc.:5 which is used in large quantities in the textile industry.
All of these have their crystal structures oriented and regulated by cooling stretching treatment and heat cent treatment, making them strong and flexible.
At 0 degrees, around 200 degrees Celsius, it's not easy.

It is well known that the crystal structure does not change and flexibility is maintained.

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
The T-coated insulated wire 7 wire is severely embrittled and cannot be put to practical use.

PET molded products are highly flexible due to the cooling rate, etc., even without the cooling stretching process, but the crystal structure changes in a few hours even at 150'C, which is relatively low compared to the processing temperature. Change and become brittle. Therefore, in order to prevent changes in the crystal structure, various functional resins are processed publicly or completely, but they gel during processing, making it impossible to stably obtain the molded product itself.

However, the present inventors have found that only compositions containing a certain type of functional resin and a Lewis acid wandering type photomixing agent capable of GFJ-initiating polymerization of the functional resin are stable to heat and are suitable for extrusion of PFT. We have finally discovered that it hardly decomposes even at processing temperatures, can be molded freely, and retains its post-ultraviolet and ultra-polymerization functions.

[Summary of the invention]

The present invention was made for the purpose of eliminating the above-mentioned drawbacks of the conventional technology.
By coating a conductor with a resin composition in which a cationic polymerization agent compound and a Lewis acid-releasing photopolymerization agent are blended into a base resin containing BT as the main component, and polymerizing it with ultraviolet light,
An object of the present invention is to provide an excellent insulated wire that can be freely molded and that does not undergo thermal embrittlement even after being treated with ultraviolet rays after the process without cooling and stretching.

[Structure of the invention]

The present invention uses a main resin mainly composed of one or more selected from PET and PBT, and two oxirane rings in one molecule.
One or more cationically polymerizable compounds, the main component of which is an epoxy resin, is added to the main resin at a concentration of z% or less, and the cationically polymerizable compound (L metallurgical light) that releases the Lewis acid catalyst by ultraviolet irradiation is added. A conductor is coated with an ultraviolet curable resin composition containing a polymerization initiator in an amount of 0.1 to 10% by weight based on the cationically polymerizable compound.
The insulated wire is then cured by ultraviolet irradiation.

The main resin used in the present invention is PET and/or PBT.
It is a resin whose main component is PET is film or f
f! Commercially available grades such as male grade or bottle grade with increased degree of polymerization by solid phase polymerization are preferred, but those containing an isophthalic acid component can also be used as long as they have a softening point of 170° C. or higher.

PBT, which is a resin similar to PET, exhibits almost the same characteristic behavior as PET, and can be used as the base material 6411 in place of PET. Only one of PET and PBT may be used, or both may be blended in an arbitrary ratio to form the main resin.

The main resin is a relatively low molecular weight hydroxy polyester resin such as Desmorchen (manufactured by Bayer AG, trade name), or Elitere (manufactured by Niji Chiriki Co., Ltd., trade name) to lower the gA degree of melt extrusion of PET and PBT. It is also possible to partially mix in a saturated copolymerized polyester resin represented by ). The main resin is a polyarylate resin known for its ability to slightly improve the thermal embrittlement of PET resins.

It may contain polycarbonate resin or polyester elastomers such as Belprene (trade name, manufactured by Toyobo Co., Ltd.) in an amount of 30% or less by weight of PET.

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. ,
Preferred are novolac type epoxy resins, alicyclic epoxy resins, and the like.

Examples of such bisphenol A epoxy resins include Nibikoat 828. Epicote 834, Epicote 836. Epicoat 1001, Epicoat 1004, Nipico-h4007 (trade names, manufactured by Shell Chemical Co., Ltd.)
, DER331, DER332, DER661, DER
664, DER667 (manufactured by Dow Chemical Company, trade names) Araldite 260, Araldite 280. Araldite 6071. Examples include Araldite 6084.7 and Araldite 6097 (trade names manufactured by Chiba Gaiki President), and these may be used alone or in combination.

Further, as the novolac type epoxy resin, for example, Epicoat 152. Epicote 154 (trade name, manufactured by Shell Chemical Co., Ltd.), Araldite EPN1138. Araldite EPN1139゜Araldite ECN1235
, Araldite ECN1273.7U/L7Dite EC
N1280. Araldite ECN1299 (manufactured by Ciba Gaiki Co., Ltd., product name), DEN431, DEN43
8 (including the Dow Chemical Company's product name, K8 product name, etc.), which may be used alone or in combination.

Further, as the alicyclic epoxy resin, for example, Araldite CY175.7 Araldite cY177, Araldite CY179. Araldite CY184, Araldite CYi92 (manufactured by Chihagaiki Co., Ltd., product names), ERL-4221゜ERL-4299, ERL
-4234 (manufactured by Union Carbide, product name)
etc. are mentioned.

They may be used alone or in combination.

In addition, it is possible to use butadiene-based epoxy resins, phenoxy resins, etc. to impart flexibility, and mixtures of the above-mentioned epoxy resins can also be used. A monofunctional epoxy diluent may be used as such a monofunctional epoxy diluent.

Examples include phenylglycidyl ether and butylglycidyl ether.

Furthermore, it is also possible to use a cationically polymerizable vinyl compound mixed with the diboxy resin.

Examples of such cationically polymerizable vinyl compounds include styrene, allylbenzene, triallyl isocyanate, triallylcyanate, vinyl ether, and N-vinylcarbazolerolidone.

The amount of cationic polymerizable compound is 50% based on the base resin.
weight percent or less.

The photopolymerization σa initiator that releases a Lewis aM medium that initiates polymerization of a cationically polymerizable compound upon irradiation with ultraviolet 7 rays used in the present invention includes -:l/J' aromatic diazonium salt;
Aromatic halonium salts, Part VI a rlA or Part ■a
- Photosensitive aromatic onium salts by Gentaka Zoku are mentioned, but aromatic halonium salts also release nitrogen gas at the same time as they release Lewis acids when irradiated with ultraviolet rays, so they are not suitable for use with electric wires. However, aromatic halonium salts, photosensitive aromatic onium salts of group Ⅰa or Vai elements, and the like are preferable.

Such an aromatic halonium salt has the general formula (()
RJd(R.)aX)E"cMQx)-"-"
(1) (wherein R4 is a monovalent aromatic organic group, R
, is a divalent aromatic organic group, and X is, for example, I, 3r,
A halogen atom such as C1, M is a full dielectric or a metalloid, a halogen atom and Q are halogen atoms, and d is 0 or 2. el
．． tO or 1, and (d+e) is equal to 2 or the valence of
(representing u), for example, C
H30 -o I+-O OCH co・BF4-
.

0- r"-0- - PR6-, CH co=C)
I +ー〇ーCH3・A s R5−
, ■+ζ)-m-ζ]・BF4-, etc.

Further, as the photosensitive aromatic onium salt of the VI a IA element or the ZVa group element, general formula (■): ((R
s)i(Ry)J(R-b”/)mi”(MQ,,)-”
"-'ゝ (II) (wherein, R6
is a monovalent aromatic organic group. R) 1 selected from the group consisting of ij-alkyl group, cycloalkyl group, and y-substituted alkyl group
aliphatic organic J1 (R. is an aliphatic organic group and an aromatic latent J3. Group 'II a elements of Se, Te or N, P, As.

Group Va element selected from sb and Bi. :A;=all metals or semimetals and Q represents a halogen atom, 1 is an integer of 0 to 4, J is a number of ○ to 2, - is a coefficient of ○ to 2, and (i + j + k ) is equal to the valence of Y, and when Y is element VI a 11A, 3.
When Y is a group Va element, it is equal to 4, i=(m-n)
holds true, and n is an integer from 2 to 7 and is equal to the valence of M, and m is an integer larger than n and less than or equal to 8), and as an onium salt of a group is [(()-)3-Sko”B F4-, [(
ζ:＞)]-Te+BiCl3-1, etc.
For example, as for ZVa group elements, CH ○ [eN-CH2-C-0 + S b F6-1 [(
kon)4-Pl” PF6-, [:(koΣ)+-A
s]" BF4-1○ [Cζn)3-P CH2C-(:>1" ASF6-
1 etc.

The Lewis a added to the cationically polymerizable compound
The amount of the M-type polymerization initiator is 0.00% of the cationically polymerizable compound.
1 to 10%, preferably 1 to 5%, O,1
If it is less than 10% by weight, the crosslinking reaction rate due to ultraviolet rays will be slow and the processing time will tend to be too long.
If it exceeds , the price of the resin composition becomes high because the catalyst cost is the crystal value.

The resin composition used in the present invention is a mixture of a recording agent resin, a cationically polymerizable compound, and a photopolymerization initiator. This resin composition can be coated on a core using a conventional extruder. Furthermore, by coating with T-dies, it is also possible to produce conductor strips or foils that have been subjected to a single-layer treatment and are used as temporary materials for electronic circuits.

After the resin 7Ml compound is released and processed, it is cured by ultraviolet crosslinking, and a pressure-transmitting mercury lamp is used for this process.

Although it may be treated in a separate process by irradiation with a light source such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp, or by electron beam irradiation, it is possible to incorporate an irradiation device into the extruder and process the resin composition after release. Shorten the water cooling tank for cooling the electric LA and cover the remainder of the first wire. It is economical to carry out the crosslinking and curing process continuously by passing the ultraviolet ray irradiated part through a return wheel once using fIJ while promoting the curing reaction by using .

[Embodiments of the invention]

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

Example I 70 parts by weight of PET pellets and 30 parts by weight of Nipicote 828 (bisphenol A type epoxy resin) were mixed,
Kneaded in a kneader at 300°C for 10 minutes, then cooled.
Pelletize, take 115 pieces of this pellet, and add 1.
The 0-layered parts are thoroughly mixed, mixed in a kneader at 250°C for 10 minutes, and then cooled and pelletized to prepare a master hatch of the initiator during the light interval.

These two pellets were thoroughly mixed in a blender, dried at 1.50°C for 30 minutes in a window airflow, and then kept at 230°C in the barrel and 260°C in the head L/D=2
8 into the hopper of the extruder, and by Kusuchenod 1
．． ○Soft mTo diameter: ii Thickness 40μ for soil extraction, line speed 50
It was pressed up at a speed of m/min to obtain a conductive gland. This electric gland is cured by ultraviolet ζ′A:q radiation treatment.

Next, the edge of this uncured mold was heated with a 2kli blind pressure water IU lamp (length 2
5ci, Iwasaki Electric Co., Ltd.) are installed at 20cm intervals, and the middle part is parallel to the length direction of the mercury lamp.
By running the wire at o+/min, an ultraviolet-cured electric wire was obtained. Table 1 shows the J-determined results of winding flexibility, softening point, and solvent resistance according to JISC3003.

Example 2 PET beret 80! Part It and 20 parts by weight of Epikote 152 (Novolank type epoxy resin) were mixed and frozen at 300°C for 510 minutes in a kneader.

Next, the pellets were cooled, and parts by weight of 1-rephenylsulfonium hexafluoro:antimobuto L, O were thoroughly mixed with the pellets, and the mixture was heated in a kneader at 250°C for 10 minutes.
The pellets were crushed, cooled, pelletized, and further dried at 150'C for 30 minutes in a nitrogen stream.

Using this pellet, the same procedure as in Example 1 was carried out to obtain a 1.0 m
M-diameter uncured coated wire and ultraviolet curing treatment! i
``An electric wire was obtained.'' The measurement results of dimensional flexibility, softening point and solvent resistance in accordance with JIS C3003 are shown in Table 1.

Example 3 PET pellets 50 ffi Q part, Tesmochen F
-950 (polyethylene terephthalate resin, manufactured by Bayer) 17 parts by weight, diethylene glycol 3 parts by weight,
30 parts by weight of Epicoat 828 was crystallized and mixed and frozen in a kneader at 300°C for 10 minutes.

Next, it was cooled and pelletized, and 115 samples of the pellets were taken and ditrilyliodonium hexafluorophosphate was added.
Sufficiently 61.0 parts by weight were mixed together and kneaded to 210"
Mix C and 1O for a minute and then cool.

Pelletize to prepare a master bunch of photopolymerization initiator. Mix these two pellets thoroughly in a blender,
Roughly dry in a nitrogen stream for 150'' C530 molecules uJ.

This Hm pellet has a barrel of 180"C and a head of 230".
The coated wire was immersed in a hopper with L/D = 28 held at C, and extruded onto a 0 mm diameter annealed copper wire to a thickness of 40 μ at a 7 wire speed of 30 i/min using a cross head. This electric wire was uncured before being subjected to ultraviolet irradiation treatment.

Then, in exactly the same manner as in Example 1, 78 pieces of insulation were obtained which were subjected to ligation and gland hardening treatment. Table 1 shows the measurement results of winding flexibility, softening point, and FJ property according to JISC3003.

Example 4 52.5 parts by weight of PET pellets, U-1o.

(Boriaarylate resin, Unitika Co., Ltd.) 17.
5 parts by weight and 30 parts by weight of Epicoat 828 were mixed, milled in a kneader to 300"C, 1O, cooled and pelletized, and the pellets were collected at 17:5 mk and trinoenylsulfonium hexafluoroantimonate. 1.0 parts by weight were thoroughly mixed, heated in a kneader for 250°C, 10 minutes, and then cooled, pelletized, and combined with light to prepare a master hatch of the initiator.

These two pellets were thoroughly mixed in a blender, dried for 30 minutes at 150°C in a nitrogen stream, and then placed in the hopper of an extruder. ○
An uncured coated electric wire of 11 mm and a J8 working wire subjected to ultraviolet curing treatment were obtained. Table 71 shows the measurement results of the windability, softening point, and 1t18 strength according to JESC3003.

Example 5 U-10017,5 weight 8++ in Example 4 is No.
varcx 7022A (polycarbonate e!j!
:, manufactured by Mitsubishi Chemical Industries, Ltd.) 17.5 parts by weight, and the other conditions were the same as in Example 4. 1.0111 m
An uncured coated electric wire with a diameter and a bag shop electric wire subjected to ultraviolet curing treatment were obtained. According to JISC30o3. with compatibility,
・Table 1 shows the Europeanization point and solvent resistance Ju determination results.

Example 6 Fruit'&Example 4 Nickel U-10017, 5'ff amount part 6 Perprene P40H (polyester elastomer,
(manufactured by Toyobo Co., Ltd.) 17.5 polymerization part, and the other conditions were the same as in Example 4. An uncured coated electric wire of 1.0 mff 1 diameter and an ultraviolet 'CA cured electric wire and a home appliance were used. , got the line. Wrapping flexibility according to JISC3003,
Table 1 shows the measurement results of the softening point and the solvent properties of the liquor.

Example 7 70 parts by weight of PET in the example was added to 1401-X (
PBT (manufactured by Toshi Co., Ltd.) was replaced with 70 parts by weight, and all other conditions were the same as in Example 1. I got it. Table 1 shows the measurement results of winding flexibility, softening point, and solvent resistance according to JISC3003.

Example 8 In a nitrogen air flow obtained in the same manner as in Example 1, 15
Dry the mixed pellets at 0℃ for 30 minutes in a barrel at 230℃.
, into the hopper of an extruder with L/D=28 held in a head 260'C, and 0.211 II by a T-type die.
Extruded with a thickness of 40μ on a copper strip with a thickness of O and a width of 50zm [
A copper strip coated on one side was obtained.

Next, this uncured seedling trunk strip was run between mercury lamps at a speed of 3 m/min in the same manner as in Example 1 to obtain a disconnected copper strip that had been irradiated with ultraviolet rays.

The total diameter of this copper strip is 18°, and the bending property is 18°.
．． Measured by placing a steel ball with a diameter of 6 m + n, applying a load of Lk on it, applying AC 100 V between the steel ball and the copper conductor, and raising the temperature at a rate of approximately ℃/min in a constant temperature bath. Table 1 shows the softening point and the solvent properties of the Japanese alcoholic beverage according to JISC3003.

Comparative Example I 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.
This was extruded onto a 01llI11 mild steel wire to a thickness of 40 μm at a wire speed of 50 for 7 minutes to obtain an insulated wire. Table 1 shows the measurement results of winding flexibility, softening point, and solvent resistance according to JISC3003.

Comparative Example 2 Using pellets of 1401-XO6 (PBT, manufactured by Toshi Co., Ltd.), a 1.0 ml, 11-diameter octagonal gland was obtained under the same conditions as in Comparative Example 1. Table 1 shows the measurement results of winding flexibility, v, other points, and solvent resistance according to JISC3003.

Comparative Example 3 75 parts by weight of PET and U-100 (boaryarylate resin,
An insulated gland with a diameter of 1.0 mm was obtained under the same conditions as in Comparative Example 1 using an extrusion mixture obtained by homogeneously kneading 25 parts (manufactured by Unitika Co., Ltd.) and pelletizing the extrusion mixture. J l5C3003
Table 1 shows the measurement results of winding flexibility, softening point, and solvent resistance according to the following.

Comparative Example 4 75 parts by weight of PET and polycarbonate resin Novare
1. x 7022A 25 fflffi part was uniformly kneaded and pelletized using an extrusion mixture under the same conditions as Comparative Example 1. An absolute electric range of diameter Oa+m was obtained. JISC3
Table 1 shows the measurement results of winding flexibility, softening point, and solvent resistance according to 0Q3.

Comparative Example 5 PET pellets were put into an extruder hopper with L/D = 28 held at a barrel temperature of 250°C and a head of 300'C, and a T-shaped die was used to spread the PET pellets onto a copper strip of 0.2 m4 and width of 50 mm. Copper strip coated on one side was obtained by extrusion coating at a thickness of 40 μm. The properties determined in the same manner as in Example 8 are shown in Table 1.

Comparative Example 6 Two parts of PET pellet 50 and two parts of Erytail UE-3221 (copolymerized polyester resin, softening point 115°C, Unitika Co., Ltd.) as a melting temperature lowering agent were mixed into P-
453 parts by weight of chlorophenol was heated and dissolved, and after returning to room temperature, gnosidyl ether of bisphenol A (room temperature viscosity 120-150 voise, epoxy equivalent 184-19
Gramdic FC-0 diacrylate of 4)
511 (Dainippon Ink & Chemicals Co., Ltd. S, Ui product name) was dissolved and dispersed in 20 parts, and then 0.4 parts by weight of 2,2-shed monoacetophenone was added as a photopolymerization initiator to form a transparent homogeneous solution. I got it.

The solvent was removed from this solution under real pressure, nitrogen gas was added, and the solution had a 4+) structure that could be discharged from the lower hole under pressure. I connected the discharge hole to a crosshead with the same mechanism used for extrusion using ordinary electric wire, and used a die and a nipple to try coating on a 1.0 ROM diameter annealed copper wire.However, the extrusion ffi paraboloid It turned into a gel, and no abducted glands were obtained.

As is clear from the results in Table 1, Comparative Example 1. Diary 5
Imaging electric wires and single-sided coated copper strips made only of PET suffer from severe thermal embrittlement and cannot be put to practical use. Also, F' is similar to PET.
13T! As shown in Comparative Example 2, the insulated wires of X-Germany also suffer from severe thermal embrittlement and cannot be put to practical use.

In Comparative Examples 3 and 4, in which a non-grade resin is mixed with PET resin in order to improve this thermal embrittlement, the thermal embrittlement is slightly improved and can withstand deterioration at 200°C for 5 hours, but After 10 hours of deterioration, embrittlement occurs, and 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.

2! In order to improve the flexibility and at the same time prevent the softening point from lowering and solvent resistance from deteriorating, the crystal is molded by extrusion processing and then cross-linked with ultraviolet rays to prevent changes caused by the heat of the crystal manufacturing process. Comparative Example 6, in which various 7-acrylate 1-based resins were blended, showed that although a copolymerized polyester resin was mixed in order to lower the melting temperature of PET, the acrylate resin remained stable even at a low melt extrusion temperature of 170°C. gelation occurs.

I couldn't get any wires.

On the other hand, in Examples 1 to 3 and 7 to 8, 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 #I 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°C is almost completely improved. I understand that.

Even in the case of a resin system in which PET is mixed with a non-grade ijI resin as in Examples 4 to 6, by using an epoxy resin and a photopolymerization initiator in combination, the insulated wire after ultraviolet irradiation treatment can be prevented from thermal embrittlement. , softening resistance, and solvent resistance are also improved.

UV irradiation according to the present invention was performed? 8-edge electric wire has mechanical strength, electricity,? It was confirmed that the insulated wire was excellent in terms of workability, coil winding processability, etc., and was extremely useful.

〔Effect of the invention〕

According to the present invention, a conductor is coated with a resin composition in which a cationic polymerizable compound and a Lewis acid free type photopolymerization initiator are blended with a base resin mainly composed of PET or PBT, and the conductor is subjected to ultraviolet polymerization.

An insulated wire that can be freely molded and has excellent softening resistance and solvent resistance without thermal embrittlement even without cold drawing treatment can be obtained.

Claims (3)

[Claims] (1) A cationically polymerizable compound whose main component is a main resin containing one or more selected from polyethylene terephthalate resin and polybutylene terephthalate resin, and an epoxy resin having two or more oxirane rings in one molecule. 50% by weight or less of the species or more based on the base resin, and 0.1 to 10% by weight of the photopolymerization initiator of the cationic polymerizable compound that releases the Lewis acid catalyst by UV irradiation based on the cationic polymerizable compound. An insulated wire characterized in that a conductor is coated with an ultraviolet curable resin composition containing the following, and then cured by ultraviolet irradiation. (2) The insulated wire according to claim 1, wherein the main resin contains 30% by weight or less of a saturated copolymerized polyester resin, a polyester elastomer, a polyarylate resin, or a polycarbonate resin. (3) The photopolymerization initiator is an aromatic halonium salt and
The insulated wire according to claim 1 or 2, which is one or a mixture of two or more selected from the group consisting of photosensitive aromatic onium salts of group Ia elements or group Va elements.