JPS61133514A - Manufacture of insulated conductor - 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] The present invention relates to a method for efficiently manufacturing insulated conductors (electric wires, conductors for forming electronic component circuits) with good characteristics.

[Prior art]

The adhesion between the conductor and the insulating layer in an insulated conductor is required to be strong enough to withstand harsh conditions such as bending during use without damaging the insulation properties. The conductor needs to have a line speed that is compatible with industrial production.

Conventionally, when manufacturing insulated conductors, especially edge-to-edge conductors, insulating tape is adhered and coated onto the conductor using a thermosetting adhesive, but in this method, the line speed is slow, so production efficiency is low. is slow and non-industrial.

In addition, a method of using a photocurable resin instead of a thermosetting adhesive has also been proposed, but the photocurable adhesive used in this case has the general formula % formula % (1) (in the formula , R1 represents a hydrogen atom or methyl, and R2 represents an esterification reaction residue of the adduct) A photoinitiator added to an acrylic group-containing compound is used, but such photocurable adhesives When using , the limit is A class insulation (105℃),
In addition, the linear speed is often slow and tends to be unindustrial.

[Problems to be solved by the present invention]

An object of the present invention is to provide a method for manufacturing an insulated conductor in which the adhesive is sufficiently cured and strongly bonded even at extremely high linear speeds.

Another object of the present invention is to have excellent heat resistance and Class B insulation (130
An object of the present invention is to provide a method for manufacturing an insulated conductor that can be heated to

[Means to solve the problem]

In the present invention, after forming a photocurable adhesive layer of a resin composition containing the following (a) and (bl), the adhesive layer of a light-transmitting film is applied so as to correspond to the conductor surface. , a method for producing an insulated conductor, characterized in that the adhesive layer is cured by irradiation with light.

(a) One or more cationic polymerizable compounds whose main component is an epoxy resin having two or more oxirane rings in one molecule.

fbl A photoinitiator in an effective amount of 05 to 10% based on the cationic polymerizable compound, which is capable of liberating a Lewis acid catalyst capable of initiating polymerization of the cationic polymerizable compound by ultraviolet irradiation.

The cationically polymerizable compound as the fat component used in the present invention is one or more cationically polymerizable compounds whose main component is an epoxy resin having 21)n or more oxirane rings in one molecule, and the epoxy resin is Bisphenol A
Preferred are type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, and the like.

Such bisphenol A epoxy resins include, for example, Epicote 828, Epicote 834, Epicote 836, Epicote 1001, Epicote 1004.
, Epicote 1007 (trade name, manufactured by Shell Chemical Co., Ltd.), DER331, DER332, DER661,
DER664, DER667, (trade names manufactured by Dow Chemical Company), Araldite 260, Araldite 28
0, Araldite 6071, Araldite 6084, Araldite) 6097 (12J top, manufactured by Chiha Geigy,
(trade name), and these can be used alone or in combination.

In addition, examples of the novolac type epoxy resin include Epikot 152, Epicoat 154 (trade name, manufactured by Shell Chemical Co., Ltd.), and Araldai) E.

PN1) 3B, Araldite I-EPN1) 39, Araldite ECN1235, Araldite ECN1273,
Araldite ECN1280, Araldite) ECN12
99 (manufactured by Ciba Geigy, product name), DEN4
No. 31, DEN438 (trade name, manufactured by Dow Chemical Company), etc., and these may be used alone or in combination.

Further, as the alicyclic epoxy resin, for example, Araldite CY175, Araldite CY177, Araldite CY179, Araldite CY184, Araldite CY192 (hereinafter referred to as "2", manufactured by Ciba Geigy, trade name)
,ER[,,-4221,ERL-4299,ERL-
4234 (trade name, manufactured by Union Carbide), etc., and these may be used alone or in combination.

Other butadiene-based epoxy resins can also be used, and mixtures of the various epoxy resins mentioned above can also be used.

A monofunctional epoxy diluent may be used in the cationically polymerizable compound as long as the curing properties are not deteriorated.

Examples of such monofunctional epoxy diluents include phenyl glycidyl ether and t-butyl glycidyl ether.

Furthermore, it is also possible to use a cationic polymerizable vinyl compound mixed with the epoxy resin, and examples of such cationic polymerizable vinyl compounds include styrene, karyoruhenzen, vinyl ether, N-vinyl hardenzene,
Examples include N-vinylpyrrolidone.

By irradiating the +bl component used in the present invention with ultraviolet rays, (
Examples of photoinitiators that release Lewis acid catalysts capable of initiating polymerization of the cationically polymerizable compound of the al component include aromatic halonium salts, photosensitive aromatic onium salts of group Vla or group Va elements, and the like. .

Such an aromatic halonium salt has the general formula (1■) 1(
R3KR41b”].L”al 7d-el (
1? ) [In the formula, R3 is a monovalent aromatic organic group, R4 is 2
The aromatic organic group X is, for example, ■, Br, Cj! , M is a metal or metalloid, Q is the same halogen atom as above, a is 0 or 2, b is 0 or 1, and (a + b) is 2 or the valence of X. , d is an integer greater than e and equal to or less than 8], for example, CI+30+I
〉OCI+3. BF;i(X...乃6, etc.).

Furthermore, as the photosensitive aromatic onium salt of Group Via element or Group Va element, general formula (III) F (R5),
(R61g(R71hYl:IMQ, 17.,
(III> [wherein, R5 is a monovalent aromatic organic group, R
6 is a monovalent aliphatic organic group selected from the group consisting of an alkyl group, a cycloalkyl group, and a substituted alkyl group, and R7 is a heterocyclic group or fused ring structure selected from an aliphatic organic group and an aromatic organic group. Constituent polyvalent organic group, Y is S, Sa, '
Group ■a elements of Fe or N, P, As, 3b and B
Group Va element selected from i, M is a metal or metalloid, and Q represents a halogen atom, f is an integer of 0 to 4, g is an integer of 0 to 2, h is an integer of 0 to 2, And (f+g
+h) is equal to the valence of Y, equal to 3 when Y is a group Vla element, equal to 4 when Y is a group Va element, and 1-(j
-k) holds true, and k is an integer from 2 to 7 and is equal to the valence of M, and J is an integer larger than k and less than or equal to 8. Examples of salts include, and examples of onium salts of Group Va elements include:
For example, etc.

ia) The amount of fdl component added to the component in the evening, f
0.5 to 10%, preferably 1 to 5% based on the al component
%, and if the amount is less than 0.5%, the ultraviolet curing speed will be slow and the curing time will tend to be too long.
If it exceeds 10%, the catalyst cost is high, so 4A+
The production cost of the fat composition is high.

The photocurable adhesive used in the present invention further has a molecular weight of 10,000 to 60% (% by weight, the same applies hereinafter) based on the thione-compatible compound C1, 000
F, Noxo resin, (d + 0.5 to 20% of hydroxyl groups in the molecule relative to the above cationic compound)
It is preferable that it contains a polyhydric alcohol.

The phenoxy resin used in the present invention (C1 component) has a molecular weight of 10,000 to 60,000 as shown by formula (1).
Examples include polymer compounds in the range of . When such a phenoxy resin is added to the (Al component), it imparts flexibility to the cured product, and as a result, it also leads to improved adhesive strength. The amount of addition is 0.5 to 20%, preferably 1 to 10% based on the Al component. If the addition amount is less than 0.5%, a sufficient addition effect cannot be obtained; If it exceeds this, the viscosity of the resin composition tends to become too high.

The method of adding the phenoxy resin to the +8+ component is as follows:
01) Heat the ingredients at a temperature of about 100 to 130°C/8
How to dissolve phenoxy resin in a solvent-1! A method such as mixing a solution obtained with the fa) component is used.

Examples of the polyhydric alcohol C of the ICL+ component used in the present invention include compounds having 2 to 42 hydroxyl groups in one molecule. Such compounds include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol. , 1,5-bentanediol, 1゜6-hexanediol, neopentyl glycol, 2.2.4-trimethylpenkune-1,3-diol, glycerin, triethylene glycol, polyethylene glycol, polycaprolactone polyol, etc. can be given. The amount of +a+component-1 of the polyhydric alcohol added is (05 to 20%, preferably (31 to 10%) based on a+acid component -1).

By adding the above-mentioned poly(1)1alnyl, the oxirane ring of the epoxy resin of the component (l) is partially anti-Ii':, and a hydroxyl group is introduced into the cured product. .

By introducing such a polar group into the cured product, the adhesive force with the conductor and the transparent tape is significantly improved. Furthermore (C1 component phenoxy resin and Idj
Due to the synergistic effect with the component polyalcohol, the adhesive strength of the cured product is greatly increased (1), and the solvent resistance is also improved.

In this specification, examples of the insulated conductor include insulated wires having round and rectangular cross sections. Note that when an insulating film is bonded to one side of a copper strip, copper foil, etc., it becomes a substrate for forming an electronic circuit.

The light-transmitting film used in the present invention may be any film that can transmit a sufficient amount of light to cure the above-mentioned photocurable adhesive. , polybutylene terephthalate is exemplified. Further, it is preferable that the light-transmitting film is in the form of a tape.

The light-transmitting film may be subjected to a chemical treatment such as electrical corona discharge treatment, ozone or oxidizing agent to make it compatible with the photocurable adhesive at IRl level.

The transparent film J1 is preferably insulating. If the insulation itself is insufficient, an insulating layer is provided between the conductor and the transparent film.

Examples of such an insulation layer of 1 m include those made of various enamel insulating layers such as polyester, polyvinyl polymer, polyurethane, nylon, polyesterimide, epoxy, epoxy-modified acrylic, and acrylic. Of course, in addition to the insulating translucent film, the above-mentioned insulating layer may be provided.

In producing the insulated conductor of the present invention, first a photocurable adhesive layer is formed on one side of a translucent film. If the photocurable adhesive is in a liquid phase at room temperature, this formation will occur as it is;
In the case of a solid phase at room temperature, a low temperature solvent (for example, acetone,
After dissolving in ethyl acetate, toluene, etc.),
This is carried out by applying a photocurable adhesive to the light-transmitting film.

Next, an adhesive layer of a light-curable adhesive J-formed transparent film is applied to the conductor surface. The coating may be done in accordance with a known method.

Next, light is irradiated to harden and set the photocurable adhesive, thereby continuously bonding the film to the conductor and the film to the film.

At this time, the linear speed is generally 2.0 to 50 m/min,
Preferably it is 10-30 m/min. As the light to be irradiated, it is preferable to use cotton (usually purple), and for that purpose, a low pressure mercury lamp, a high TIE mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, etc. are used. The intensity of light is at least O, OO2 watts/c+ at sunset
If it's A Kl l2, it's a minute.

At the time of photocuring, it may be heated to about 50 to 200°C, in which case the photocuring reaction is accelerated.

Examples 1 to 5, Comparative Examples 1 to 4 Using the adhesive, insulating (tape-like) film, and conductor shown in Table 1, warp thread-colored edge conductors were manufactured under the conditions shown in Table 1. I informed you.

For the vertically insulated conductors with iM in Test Examples and Comparative Examples, the breakdown voltage O, L, J by each tin foil wrapping method was determined.
Wrapping properties were tested in accordance with IS C-3003.

(Note) If a vertical insulated conductor is wrapped 1 times i (1d), the film will peel off and float if the adhesion between the conductor and the film or between the films (wrapping edges) is poor. In Table 1, this is expressed as defective.

In the case of a square conductor, set it along the rod of 4 smφ,
-Wise bending 180° and the same judgment was made.

Description of each adhesive in Table 1: A: Araldai 1-cY-179 (cycloaliphatic epoxy 48
4 fat) to 95 parts (by weight, the same applies hereinafter) and PKI
5 parts of phenoxy resin (manufactured by Union Car Hi R) to 12
Heating at 0℃/mixing for 8 stations, after cooling to 40-50℃,
A mixture of 5 parts of diethylene glycol and 1-2 parts of l-riphenylsulfonium and 1-2 parts of difluoroantimony. 1') were heated and mixed at 130°C, and after cooling to 40-50°C, 10 parts of glycerin and 1-2 parts of triphenylsulfonium hexafluoroantimone were dissolved and mixed. .

C: E R1, -4299 (alicyclic epoxy resin)
90 parts of PKIIHIO were heated and mixed at 120°C, cooled to 40-50°C, and 3 parts of ethylene glycol and 3 parts of diphenyliolinium hexafluorophore I was dissolved. A combination of two things.

D: To 82898 parts of Ebico-1, add 40 to 5 parts of triphenylsulfonium hexafluoroantimo 2-1.2.
Dissolved and mixed at 0℃.

E: Ωzuray PC-Exp8530 Evokin acrylate type photo-curing paint large l'' Manufactured by Honink Kagaku Kogyo Co., Ltd. F: 9 5 0 5 parts of P K II C were heated and mixed at 130°C, and after cooling to room temperature, 2 parts of 4MZ (imidazole curing agent, manufactured by Shikoku Kasan Nirigyo) were mixed.
A product made by kneading and homogenizing parts.

〔Effect of the invention〕

According to the present invention, it is possible to manufacture an insulated wire at an extremely high wire speed, and the insulated conductor thus manufactured has a transparent film strongly adhered to the conductor, and has excellent heat resistance. It is.

This point will be specifically explained based on the test results. That is, (a+Comparative Example 4) Compared to (normal catalytic epoxy adhesive), Example 1 can achieve a linear velocity 7 times higher.

lbl Example 1 and Comparative Example 1 (rectangular conductor) and Example 2
．． 3.4 and Comparative Example 2.3 (round wire), although there is not much difference in manufacturing speed, the windability after deterioration at 200°C is
The present invention is significantly superior.

(In the case of C1 Example 5, since phenoxy resin and polyhydric alcohol were not added, the winding property after 10 hours of 200" C3 was not very good at 5d Good, but it was still better than L Comparative Example 2.3. It's extremely good.

(Margin below)

Claims (5)

[Claims] (1) A photocurable adhesive layer made of a resin composition containing the following (a) and (b) was formed on one side of a transparent film, and the adhesive layer was applied to correspond to the conductor surface. A method for manufacturing an insulated conductor, comprising: curing the adhesive layer by irradiating the adhesive layer with light. (a) One or more cationic polymerizable compounds whose main component is an epoxy resin having two or more oxirane rings in one molecule. (b) 0.5 to 10% of the cationically polymerizable compound (
% by weight) of an effective amount of photoinitiator. (2) The resin composition further has a molecular weight of 0.5 to 20% relative to the cationic polymerizable compound (c) of 10,000.
phenoxy resin and/or (d
) The insulated conductor according to claim (1), which contains a polyhydric alcohol having two or more hydroxyl groups in the molecule in an amount of 0.5 to 20% based on the cationically polymerizable compound. Production method. (3) The method for manufacturing an insulated conductor according to claim (1), characterized in that heating is performed together with light irradiation when curing the photocurable adhesive. (4) A method for producing an insulated conductor according to claim (1), wherein an insulating layer is provided between the conductor and the transparent tape. (5) A method for manufacturing an insulated conductor according to claim (1), wherein the light-transmitting tape has its affinity with an adhesive improved by chemical treatment or electrical corona discharge treatment.