JPH06150725A - Wire and manufacture thereof - Google Patents

Abstract

PURPOSE:To enhance the insulating property, water and oil repellency and antifouling property of wire and to greatly reduce the time for drying after washing process subsequent to soldering by forming a chemical adsorption film on a conductor or a coated wire. CONSTITUTION:A chlorosilane surface active agent is brought into contact with a conductor or a coated wire 1 in an organic solvent or dry gas. Then dechlorination occurs between a hydrophilic group on the surface of the conductor or the coating and the chlorosilyl group of the surface active agent and a chemical adsorption film (3, 4) is formed by siloxane bonding 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric wire having a chemisorption film formed on its surface and a method for manufacturing the electric wire. More specifically, an electric wire in which a chemisorption film molecule having a functional group capable of reacting with a hydrophilic group at the end is reacted with a conductor wire or a coated electric wire to form a chemisorption film having a siloxane bond by the molecule, The manufacturing method is related.

[0002]

2. Description of the Related Art Conventionally, in the electric and electronic industries, electric wires have been used for coils, inductors, transformers, armatures, solenoids, and other windings, lead wires, etc. Insulated and protected by coating material. To cover the electric wire, a method of immersing it in a liquid bath of resin or extruding a solid thermoplastic resin onto the electric wire is used.

Since a relatively thick film can be formed by coating PVC polyethylene, polytetrafluoroethylene or the like by an extrusion method, it is used for connection and lead wires. The dip coating method can be used as a thin film, so it is used to insulate thin magnet wires and to impregnate coils and windings.

When these wires are actually used, the ends of the wires are bonded by soldering or the like.
After soldering, in order to remove the residual flux, cleaning is performed with chlorofluorocarbon, 1,1,1-trichloroethane or the like. If there is residual flux,
This is because deterioration of electric insulation, short circuit, migration and the like occur.

[0005]

The conventional coating film for electric wire uses various insulating materials depending on its application, but each has its advantages and disadvantages. For example, polyurethane and nylon have solvent resistance, but have a heat resistance temperature of 10
Not too high at 5 ° C and highly hygroscopic. Also, polytetrafluoroethylene, which has high heat resistance, has low adhesion,
The thermal softening property under high load is remarkably poor, and the coating film also lacks hardness. Polyimide also has a high heat resistance, but it is less susceptible to hydrolysis when high humidity conditions overlap.

In addition, chlorofluorocarbons, 1,1,1-trichloroethane, etc., which have been used for cleaning up to now, have been limited in production and use in order to protect the global environment, and have already been decided to be totally abolished. Therefore, non-water-based or water-based cleaning as a non-cleaning method or a CFC alternative cleaning method is being studied. It is ideal to use no-clean flux or no-cream cream solder for cleaning, but it has not yet been put to practical use in terms of solderability and reliability. Further, in the case of a non-aqueous detergent, there is a problem that it is difficult to handle industrially because it requires an explosion-proof facility because it has a flash point. Further, when an aqueous cleaning agent is used, there is a problem in that wastewater treatment is required and drying property is required. Further, when the winding is washed, it is difficult to dry the water or solvent that has entered the winding, and it takes a long time.

In order to solve the above-mentioned conventional problems, the present invention provides a wire formed by a chemical adsorption film in which a film molecule and a conductor wire molecule are chemically bound to each other, or an electric wire already coated with a coating film. An object of the present invention is to provide an electric wire and a manufacturing method thereof, which can improve heat resistance, moisture absorption resistance, insulation, etc. by forming a chemical adsorption film, and can shorten drying after a washing step for flux removal.

[0008]

In order to achieve the above object, the first electric wire of the present invention has a structure in which a chemical adsorption film is formed on the surface of the conductor wire through a siloxane bond.

Next, the second electric wire of the present invention has a structure in which a chemical adsorption film is formed through a siloxane bond on the insulating coating applied to the bare electric wire. In the above structure, it is preferable that the chemisorption film molecule contains a fluorinated alkyl group or an alkyl group.

Further, in the above structure, the chemical adsorption film is preferably a monomolecular film. Next, the first production method of the present invention is a method in which a chemisorption molecule having a functional group that reacts with a hydrophilic group at the end is dissolved in a non-aqueous solvent, and an electric wire coated with a conductor wire or an insulating coating is prepared. It is characterized in that the chemical adsorption molecule is brought into contact with the conductor wire or the electric wire coated with an insulating film to cause a low molecule desorption reaction to form a chemical adsorption film through a siloxane bond.

Next, in the second production method of the present invention, a solution comprising a chemisorption molecule having a functional group that reacts with a hydrophilic group at the terminal is gasified, and the chemisorption molecule and the conductor wire or the insulating coating are formed. It is characterized in that a coated electric wire is brought into contact with it to cause a low-molecular elimination reaction to form a chemisorption film via a siloxane bond.

[0012]

According to the structure of the first electric wire of the present invention, since the conductor wire surface molecule and the chemisorption film molecule form a siloxane bond, insulation and protection with a strong bonding force, even though it is an ultrathin film. A chemical adsorption film with functions can be realized. The water and oil repellency of this film has an antifouling effect, and the drying process after the washing process can be greatly shortened. Furthermore, it is not necessary to newly form a coating film or the like for the purpose of electrical insulation and protection.

According to the second electric wire structure of the present invention, the water-repellent and oil-repellent property of the chemical adsorption film on the surface of the insulating coating applied to the electric wire can greatly shorten the drying step after the washing step. In addition, the electric wire protection and insulation function can be improved.

Further, according to the preferable constitution of the present invention in which the chemical adsorption film molecule has a fluorinated alkyl group or an alkyl group, the fluorinated alkyl group or the alkyl group is located on the surface of the chemical adsorption film. Therefore, characteristics such as electric insulation, water / oil repellency, heat resistance, and chemical resistance can be further improved.

Further, according to the preferable constitution of the present invention in which the chemisorption film is a monomolecular film, the film thickness can be made extremely thin within the range of nanometer level or angstrom level, so that the surface of the conductor wire or the coating film is coated. Even if there are irregularities, a film can be formed sufficiently uniformly, pinholes are few, and cracks are suppressed. Further, it is possible to reduce the volume of the winding or the like.

According to the structure of the first production method of the present invention, the low molecular desorption between the chemisorption film molecule having a chlorosilyl group at the terminal and the hydrophilic group on the conductor wire or the coating film. Since a film is formed in an organic solvent by utilizing a reaction (for example, dehydrochlorination reaction), the reaction proceeds rapidly and a chemisorption film can be formed in a short time. Moreover, since it is not necessary to apply much temperature, it does not adversely affect the conductor wire and the coating film.

Further, according to the structure of the second manufacturing method of the present invention, since the film is formed in the vapor phase, the conductor wire or the coating film is not damaged by the organic solvent.
Further, since it is not necessary to heat the electric wire, it is not easily affected by heat.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following examples. A conceptual cross-sectional view of one embodiment of the electric wire of the present invention is shown in FIG.
As shown in (1), the chemical adsorption film 3 is bonded to the surface of the conductor wire 1 through the siloxane bond 2. Reference numeral 4 is a chemisorption monomolecular film 4 in which the siloxane bond 2 and the chemisorption film 3 are combined.

Further, FIG. 2 shows a conceptual sectional view of another embodiment of the electric wire of the present invention. A coating film 5 is applied on the conductor wire 1, and a chemisorption monomolecular film 4 is further formed.

The chemisorption membrane molecules used in the present invention are fluorinated.
Alkyl groups or chlorosilanes containing alkyl groups
It is composed of a surfactant. Fluorinated alkyl group
The following chlorosilane-based surfactants have
Can be mentioned as an example. (1) Examples of trichlorosilane-based surfactant CF₃(CF₂)₇(CH₂)₂SiCl₃, CF₃C
H₂O (CH₂)₁₅SiCl₃, CF₃(CH₂)₂S
i (CH₃)₂(CH₂)₁₅SiCl₃, F (CF₂)
_Four(CH_{twenty two}Si (CH₃)₂(CH₂)₁₅SiCl
₃, F (CF₂)₈(CH₂)₂Si (CH₃)₂(C
H₂)₁₅SiCl₃, CF₃COO (CH₂)₁₅SiC
l₃, CF₃(CF₂)_Five(CH₂)₂SiCl₃． (2) Lower alkyl group-substituted monochlorosilane type or
Dichlorosilane-based surfactant (where n in the formula is 1
Or 2) CF₃(CF₂)₇(CH₂)₂SiCl_n(CH₃)
_3-n, CF₃(CF₂)₇(CH₂)₂SiCl_n(C
₂H_Five)_3-n, CF₃CH₂O (CH₂)₁₅SiCl_n
(CH₃)_3-n, CF₃CH₂O (CH₂)₁₅SiCl
_n(C₂H_Five)_3-n, CF₃(CH₂)₂Si (C
H₃)₂(CH₂)₁₅SiCl_n(CH₃)_3-n, CF
₃(CH₂)₂Si (CH₃)₂(CH₂)₁₅SiCl
_n(C₂H_Five)_3-n, F (CF₂)₈(CH₂)₂Si
(CH₃)₂(CH₂)₉SiCl_n(CH ₃)_3-n，
F (CF₂)₈(CH₂)₂Si (CH₃)₂(C
H₂)₉SiCl_n(C₂H _Five)_3-n, CF₃COO
(CH₂)₁₅SiCl_n(CH₃)_3-n, CF₃COO
(CH₂)₁₅SiCl_n(C₂H_Five)_3-n， Of these, especially trichlorosilane-based surfactants,
A chlorosilane other than the chlorosilyl group bonded to the hydrophilic group
The rilyl group is separated from the adjacent chlorosilyl group by a siloxane bond.
A stronger chemisorption film due to the formation of intermolecular bonds
preferable.

Furthermore, if a double bond group or a triple bond group is incorporated in the fluorinated alkyl chain or the alkyl chain portion,
After the chemical adsorption film is formed, it can be crosslinked by electron beam irradiation of about 5 megarads, so that the strength of the chemical adsorption film can be improved.

Examples of the chlorosilane-based surfactant having an alkyl group include CH ₃ (CH ₂ ) ₁₈ SiC.
l ₃ , CH ₃ (CH ₂ ) ₁₅ SiCl ₃ , CH ₃ (C
_{H 2) 10 SiCl 3, CH} 3 (CH 2) 25 SiCl including trichlorosilane-based surface active agents such as _3, for example, _{CH 3 (CH 2) 18 SiCl} n (CH 3) 3-n, CH
₃ (CH ₂ ) ₁₈ SiCl _n (C ₂ H ₅ ) _3-n , CH
_{3 (CH 2) 15 SiCl n} (CH 3) 3-n, CH 3 (C
_{H 2) 10 SiCl n (CH} 3) 3-n, CH 3 (CH 2)
Examples thereof include lower alkyl group-substituted monochlorosilane-based or dichlorosilane-based surfactants such as ₂₅ SiCl _n (C ₂ H ₅ ) _3-n (where n is 1 or 2 in the formula).

The chlorosilane-based surfactant applicable to the present invention is not limited to the linear molecule as described above, but may be a fluorinated alkyl group or a branched alkyl group, or a fluorinated alkyl group or a fluorinated alkyl group at the terminal silicon. A form substituted with an alkyl group (that is, R, R ¹ , R ² , and R ³ are fluorinated alkyl groups or alkyl groups, and are represented by the general formula R ₂ SiC
l ₂ , R ₃ SiCl, R ¹ R ² SiCl ₂ , R ¹ R ² R
³ SiCl, etc.). However, linear molecules are more preferable in order to increase the density of the chemisorption film.

Further, for example, SiCl_Four, SiHCl
₃, SiH₂Cl₂, Cl (SiCl₂O)_nSiCl
₃(Where n is a natural number), SiCl_m(C
H₃)_4-m, SiCl_m(C₂H_Five)_4-m(However, m in the formula
Is an integer of 1 to 3), HSiCl_k(CH ₃)_3-k, HS
iCl_k(C₂H_Five)_3-k(However, k is 1 or 2 in the formula)
A molecule containing a plurality of chlorosilyl groups such as
After reacting with the protective film manufacturing method, it is reacted with water
And the chlorosilyl group on the surface is placed on the hydrophilic silanol group.
Thus, the surface of the electric wire becomes hydrophilic.

Of these, tetrachlorosilane is more preferable because it has a high reactivity and a small molecular weight, so that it can give silanol groups at a high density. As a result, the chemical adsorption film molecules are also densified, so that the insulating property and the protective function can be improved.

The conductor wire used in the present invention and the electric wire coated with a coating film have, for example, --OH groups or --CO on the surface.
OH groups, -NH ₂ group,> may be any line that contains a hydrophilic group such as a NH group. As an example, for example, copper wire,
There are conductor wires such as copper alloy wires, aluminum wires, and steel wires, enamel wires, glass-wound copper wires, cotton, silk-wound copper wires, and coated film electric wires such as synthetic resin insulated electric wires. However, in the case of a conductor wire having a small number of hydrophilic groups on the surface and an electric wire coated with a coating film, for example, chemical treatment by a usual means such as ozone oxidation or electron beam irradiation, or tetrachlorosilane treatment as described above, etc. By increasing the number of hydrophilic groups, a conductor wire more suitable for the present invention and an electric wire coated with a coating film can be obtained.

The organic solvent used in the first production method of the present invention is a non-aqueous organic solvent which has as little water as possible since the chemisorption film molecule reacts with the water-based molecule and does not attack the conductor wire or the coating film. Any solvent may be used as long as it can sufficiently dissolve the molecules of the chemisorption film. For example, a fluorine-based solvent composed of a linear molecule having a fluoroalkyl group, or a fluorine-based solvent such as a tertiary amine having a fluoroalkyl group or a cyclic ether having a fluoroalkyl group, such as hexane, octane, hexadecane, or cyclohexane. A hydrocarbon solvent, for example, an ether solvent such as dibutyl ether or dibenzyl ether, for example, an ester solvent such as methyl acetate, ethyl acetate, isopropyl acetate or amyl acetate is preferable.
Examples of the ketone solvent include acetone and methyl ethyl ketone.

Next, in the second manufacturing method (vapor phase method) of the present invention, for example, the printed circuit board is placed in a vacuum container and the internal atmosphere is made high vacuum or is replaced with dry air or dry nitrogen gas. To a dry atmosphere, and then the chemisorbed molecules are supplied in a gas state to cause a low-molecular desorption reaction (for example, dehydrochlorination reaction) on the surface of the printed board to form a chemisorbed film. In this case, since no solution is used, it is less susceptible to contamination.

Further, the chemical adsorption film of the present invention can obtain a sufficient function even with only one monomolecular film. In order to form a monolayer, if an organic solvent is used, it is adsorbed with a chlorosilane-based surfactant or a molecule containing multiple chlorosilyl groups, and then an excess of non-aqueous organic solvent is used without contact with moisture. The adsorbed molecules may be washed. Further, when forming the chemisorption film in the gas phase, such a washing step is not necessary and the monomolecular film can be easily formed. Further, it goes without saying that a chemical adsorption film in which such a monomolecular film is accumulated to increase the film thickness may be used. Furthermore, the polymer adsorption film can be formed by omitting the washing step with the non-aqueous solution. The present invention may be an adsorption film of such a polymer.

The present invention will be described in more detail with reference to specific examples. Example 1 First, heptadecafluorodecyltrichlorosilane, which is a chlorosilane-based surfactant containing a fluorinated alkyl group, was used as the chemisorption film molecule.

A copper wire having a diameter of 0.4 mm was used as the conductor wire. The copper wire was immersed in a cyclohexane solution containing the chemical adsorption film molecule at a concentration of 10 ^-2 mol / l for 60 minutes at room temperature in a nitrogen atmosphere.

Subsequently, unreacted heptadecafluorodecyltrichlorosilane was washed with cyclohexane and further with pure water to form a chemisorption monomolecular film. The thickness of the resulting chemisorption monolayer was about 15 Å.

In addition, several copper wires which have been subjected to the above treatment are stacked,
When the contact angle was measured, the contact angle of water was about 120 degrees. Furthermore, when the insulation resistance of the treated copper wire was measured, the dielectric strength was 5 × 10 ⁶ V / cm even though it was a monomolecular film.
A ^leak current of 8 × 10 ⁻¹² A / V · cm was obtained. This withstand voltage was sufficiently high as compared with the withstand voltage of 2 × 10 ⁶ V / cm of the ethylene tetrafluoride film having a film thickness of 2.5 × 10 ⁻³ cm.

Also, this copper wire is used for a wire with a diameter of 3.0 mm.
It was wrapped 00 times, immersed in water for 5 minutes, and exposed to ultrasonic waves with a frequency of 45 kHz. Then take out the wire together,
It was put in a dryer at 100 ° C. and dried. When the drying time was measured by the gravimetric method, it was dried in about 10 minutes.

As a comparative example, a similar winding was prepared using a copper wire on which a chemisorption film was not formed, and the drying time was measured. The inside of the winding could not be dried sufficiently even after drying for 10 hours. It was

Example 2 The same experiment as in Example 1 was conducted, except that heptadecafluorodecyltrichlorosilane was replaced with tridecafluorooctyltrichlorosilane in Example 1. However, this time, unreacted tridecafluorooctyltrichlorosilane remaining on the copper wire was immersed in methanol for reaction instead of being washed with cyclohexane.

In this case, the film thickness of the chemisorption film was about 100 Å, and the contact angle of water was about 110 °. Also, withstand voltage 6 × 10 ⁶ V / cm, leak current 8 × 10
^{It was −12} A / V · cm, and when the drying property was examined in the same manner as in Example 1, it was dried in about 10 minutes.

Example 3 Next, an enameled wire having a diameter of about 0.5 mm was used in a nitrogen atmosphere for 2 hours.
It was taken out after being exposed to the perfluorododecyltrichlorosilane solution heated to 60 ° C. for a period of time.

As a result, an electric wire having a withstand voltage of 7.5 × 10 ⁶ V / cm and a leak current of 8 × 10 ⁻¹² A / V · cm was obtained. When the drying property was examined in the same manner as in Example 1, It dried in about 15 minutes.

[0040]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, since the surface of the conductor wire or the surface of the insulating coating and the molecule of the chemisorption film form a siloxane bond, the film has a strong bonding force even though it is an ultrathin film. An electric wire with insulation and water and oil repellency can be formed. Therefore, it has an insulation function equal to or higher than that of the conventional insulating coated electric wire, and can reduce the volume of the winding wire and the like, which enables miniaturization and weight reduction of parts, which is industrially useful.

Further, the antifouling effect is improved, and the drying process after the washing process can be greatly shortened. Further, the method for producing an electric wire of the present invention makes it possible to easily form a coating film and provide a method for producing an electric wire in which the influence of a solvent or heat on a conductor wire or an insulating coating is small.

[Brief description of drawings]

FIG. 1 is a conceptual cross-sectional view in which a chemical adsorption film is formed on a conductor wire which is an embodiment of the present invention through a siloxane bond.

FIG. 2 is a conceptual cross-sectional view in which a chemical adsorption film is formed on a wire provided with a coating film, which is another embodiment of the present invention, through a siloxane bond.

[Explanation of symbols]

 1 Conductor wire 2 Siloxane bond 3 Chemical adsorption film 4 Chemical adsorption monomolecular film 5 Coating film

Claims (6)

[Claims] 1. An electric wire in which a chemisorption film is formed on the surface of a conductor wire through a siloxane bond. 2. An electric wire in which a chemical adsorption film is formed via a siloxane bond on an insulating coating applied to a bare electric wire. 3. The electric wire according to claim 1, wherein the chemisorption film molecule contains a fluorinated alkyl group or an alkyl group. 4. The electric wire according to claim 1, wherein the chemisorption film is a monomolecular film. 5. A chemisorption molecule having a functional group that reacts with a hydrophilic group at the end is dissolved in a non-aqueous solvent, and a conductor wire or an electric wire coated with an insulating coating is immersed in the chemisorption molecule to obtain the chemisorption molecule. The low-molecular elimination reaction is caused by contacting the conductor wire or the electric wire coated with an insulating film,
A method for producing an electric wire, which comprises forming a chemisorption film through a siloxane bond. 6. A low-molecular-molecule desorbed by gasifying a solution of a chemisorption molecule having a functional group that reacts with a hydrophilic group at the terminal and contacting the chemisorption molecule with a conductor wire or an electric wire coated with an insulating film. A method for producing an electric wire, which comprises causing a reaction to form a chemisorption film through a siloxane bond.