CN1291421C - Method for forming polymer plating layer and metal conductor with isolation plating layer - Google Patents
Method for forming polymer plating layer and metal conductor with isolation plating layer Download PDFInfo
- Publication number
- CN1291421C CN1291421C CNB991054709A CN99105470A CN1291421C CN 1291421 C CN1291421 C CN 1291421C CN B991054709 A CNB991054709 A CN B991054709A CN 99105470 A CN99105470 A CN 99105470A CN 1291421 C CN1291421 C CN 1291421C
- Authority
- CN
- China
- Prior art keywords
- metallic conductor
- plating layer
- electrode
- aqueous solution
- alkaline aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- 238000000034 method Methods 0.000 title claims description 75
- 238000007747 plating Methods 0.000 title claims description 37
- 229910052751 metal Inorganic materials 0.000 title abstract description 10
- 239000002184 metal Substances 0.000 title abstract description 10
- 238000002955 isolation Methods 0.000 title 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/16—Insulating conductors or cables by passing through or dipping in a liquid bath; by spraying
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
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Abstract
一种产生聚合镀层的方法，包括以下步骤：将金属导体浸泡在碱性水溶液中，所述碱性水溶液包含具有C4位未被取代基取代和C2、C3、C5和C6位被取代基取代或未被取代基取代的苯酚衍生物和烷基胺，用金属导体作为电极对苯酚衍生物进行电解聚合。
A method for producing a polymeric coating, comprising the steps of: immersing a metal conductor in an alkaline aqueous solution, the alkaline aqueous solution comprising a C4 position that is not substituted by a substituent and a C2, C3, C5, and C6 position that are substituted by a substituent or Phenol derivatives and alkylamines not substituted by substituents are electrolytically polymerized with metal conductors as electrodes.
Description
Technical field
The present invention relates to obtain the polymer plating layer and the coating production method thereof of organic polymer with the electrolysis polymerization method.The invention still further relates to metallic conductor by using described generation polymer plating layer method on metal material, to form the method for insulating blanket and be coated with this insulating blanket.The invention still further relates to method at wire coil or analog surface generation electric insulating copolymer coating.
Background technology
Electronic apparatus was rapidly to miniaturization, high performance development in recent years.This has just formed the demand as the miniaturization of the coil of these appliances components and parts and performance enhancing.Be filled within the confined space owing to be coated with a large amount of leads of insulating blanket, therefore require plain conductor that thin insulating blanket is arranged.When a large amount of leads is filled within the confined space, its insulating blanket of lead that is coated with insulating blanket most possibly sustains damage, and for example may be caused by the pin of automatic coil winding machine or the like institute, therefore has local ground connection shortage and the not enough problem of ground connection.
In the field of the lead of tape insulation coating, especially have the lead of square-section, the someone proposes to have the lead of the insulating barrier of quite thick for example 8-20 micron always.Usually, be drawn as line sample shape metallic conductor and dry the lead that above-mentioned composition is produced tape insulation coating by insulating varnish is put on.In the field of insulating blanket lead, never develop only several microns of its thickness or insulating blanket lead still less with square-section.Its reason is, though might be by to applying the thin insulating blanket that paint and follow-up oven dry are optimized two main planes that form the rectangular metal conductor,, the stable thin insulating coating of formation still has difficulties on the end face of metallic conductor.In addition, might produce the lead of tape insulation coating by on metallic conductor, forming insulating blanket and roll-in said composition with circle with square-section.Yet because there is such problem in tape insulation coating lead some residual pressure in its insulating blanket of producing in this way, insulating blanket is given birth to crackle easily, especially when the insulating blanket that adopts big roll-in speed or produced is thin.As a result, withstand voltage and/or thermal shock impedance may be subjected to very big infringement.
In a kind of possible method that forms thin insulating blanket on the metallic conductor is exactly the thin polymer coating that forms electric insulating copolymer by electrolysis polymerization on metallic conductor, and wherein, metallic conductor is as electrode.For example, Electrochimica Acta, 22,451-457 page or leaf (1977) and Journal of AppliedElectrochemistry, 9, the method that forms electric insulating copolymer coating with the electrolysis polymerization method on metallic conductor was disclosed in the file of 483-493 page or leaf (1979).
As mentioned above, because a large amount of lead often get jammed in the confined space so that winding volume minimizes and improves performance, the insulating blanket lead that has thin insulating blanket is sought after.Electrolysis polymerization is a kind of feasible method that forms thin insulating blanket.In addition, in addition when the insulating blanket lead because the jammed result who advances the confined space of a large amount of leads makes its insulating blanket be subjected to continuing to damage, also can be easy to repair this any insulation defect by electrolysis polymerization in the impaired part of insulating blanket metallic conductor.
But the traditional electrical method that depolymerizes is only prepared with iron as metallic conductor.In addition, because electrolysis polymerization has produced the polymer plating layer of electric insulation, conductivity is interrupted along with the growth of electrode polymer coating, the feasible polymer plating layer that is difficult to be formed with adequate thickness.
Summary of the invention
According to the present invention, a kind of method that is used to produce polymer coating is provided, comprise following steps: metallic conductor is immersed in the alkaline aqueous solution, and described alkaline aqueous solution comprises and has the C4 position and be not substituted basic replacement and C2, C3, C5 and C6 position and be substituted base and replace or be not substituted phenol derivatives and the alkylamine that base replaces; And carry out electrolysis polymerization as the electrode pair phenol derivatives with metallic conductor.
Perhaps, this method that is used to produce polymer plating layer according to the present invention, may further comprise the steps: metallic conductor is immersed in the alkaline aqueous solution, and described alkaline aqueous solution comprises and has the C4 position and be not substituted basic replacement and C2, C3, C5 and C6 position and be substituted base and replace or be not substituted phenol derivatives, the polymerisable monomer with unsaturated C-C key and the alkylamine that base replaces; And with metallic conductor as the electrode pair phenol derivatives with have unsaturated C-C key polymerisable monomer and carry out electrolysis polymerization.
Perhaps, this method that is used to produce polymer plating layer according to the present invention, may further comprise the steps: metallic conductor is immersed in the alkaline aqueous solution, described alkaline aqueous solution comprises and has the C4 position and be not substituted in basic replacement and C2, C3, C5 and the C6 position at least one and be substituted the phenol derivatives that base replaces, wherein, at least one in the described substituting group has a unsaturated C-C key; And carry out electrolysis polymerization as the electrode pair phenol derivatives with metallic conductor.
Perhaps, this method that is used to produce polymer plating layer according to the present invention, may further comprise the steps: metallic conductor is immersed in the alkaline aqueous solution, described alkaline aqueous solution comprises and has the C4 position and be not substituted in basic replacement and C2, C3, C5 and the C6 position at least one and be substituted phenol derivatives and the polymerisable monomer that base replaces, wherein, at least one in the described substituting group has a unsaturated C-C key; And carry out electrolysis polymerization as electrode pair phenol derivatives and polymerisable monomer with metallic conductor.
In one embodiment of the invention, metallic conductor is the metallic conductor that its composition comprises copper.
In another embodiment of the present invention, this method also comprises, the metallic conductor that is formed with polymer plating layer after described electrolysis polymerization step on it is immersed in water or any non-alkaline aqueous solution or the step in the alcoholic solution.
In another embodiment of the present invention, this method also comprises, the step that after described electropolymerization step the polymer plating layer that is produced by electrolysis polymerization is heated.
In another embodiment of the present invention, described metallic conductor is coated with electric insulation coating, and this insulating blanket comprises defect part.
In another embodiment of the present invention, alkaline aqueous solution comprises and has the C4 position and be not substituted in basic replacement and C2, C3, C5 and the C6 position at least one and be substituted the phenol derivatives that base replaces, wherein, at least one in the described substituting group thing group has unsaturated C-C key, and comprises alkylamine.
In another embodiment of the present invention, the C4 position of phenol derivatives is not substituted that base replaces and in C2, C3, C5 and the C6 position at least one is substituted base and replaces, wherein, at least one that is substituted in the group has unsaturated C-C key, and this phenol derivatives is 2-chavicol, 2-(1-acrylic) phenol or 2 pi-allyls-6 methylphenol.
According to another aspect of the present invention, a kind of metallic conductor that has insulating blanket to cover is provided, it comprises: metallic conductor, and the polymer coating that any method forms on the part or all of surface of metallic conductor according to the method described above.
Described like this, in this article the present invention has following advantage: 1) the thin insulating blanket that firmly is formed on the metallic conductor is provided; 2) provide the insulating blanket that on the metallic conductor of for example copper, forms, and this is unapproachable to traditional electrolysis polymerization method; 3) method that provides the insulation defect on the metallic conductor that insulating blanket is covered to repair; And 4) provide a kind of production to have the method for the lead of thin insulating blanket covering.
These and other advantages of the present invention after the reading and understanding that those skilled in the art describe in detail below 1 pair with reference to figure, can become apparent.
Description of drawings
Fig. 1 is the schematic diagram that explanation is used to produce the equipment of polymer plating layer, and this equipment is by being used according to the generation polymer plating layer method in the example 12 of the present invention.
Embodiment
Below, the method according to generation polymer plating layer of the present invention is described.
According to a first aspect of the present invention, a kind of method that produces polymer plating layer is provided, it may further comprise the steps: metallic conductor is immersed in the alkaline aqueous solution, and described alkaline aqueous solution comprises and has the C4 position and be not substituted basic replacement and C2, C3, C5 and C6 position and be substituted base and replace or be not substituted phenol derivatives and the alkylamine that base replaces; And carry out electrolysis polymerization as the electrode pair phenol derivatives with metallic conductor.Below, this method is described.
Having the C4 position is not substituted basic replacement and C2, C3, C5 and C6 position and is substituted the replaceable group that base replaces or be not substituted C2, C3, C5 and C6 position in the phenol derivatives that base replaces and comprises following group and be not limited to C2, C3, C5 and C6 bit substituent: the aliphatic hydrocarbon group of the saturated or undersaturated 1-12 of having carbon atom, 1-7 carbon atom preferably, or have the aromatic hydrocarbon group of 6-12 carbon atom; Alkoxyl (RO-); Alkoxyalkyl (ROR-); Acyl group (RCO-); Alkoxy carbonyl (ROCO-); Amide group (RCONH-); Carbamyl alkyl (H
2NCOR-); And hydroxy alkyl (HOR-); Wherein, R represents to have unit price or two valency alkyl of 1-12 carbon atom, preferably 1-7 carbon atom.
As for alkylamine, preferably use monoalkylamine, dialkylamine or trialkylamine with 1-4 carbon atom, for example, methylamine, ethamine, n-propylamine, isopropylamine, n-butylamine, isobutyl amine, t-butylamine, dimethylamine, diethylamide, two (n-third) amine, two (different third) amine, two (n-fourth) amine, two (isobutyl) amine, two (t-fourth) amine, trimethylamine, triethylamine, three (n-third) amine, three (different third) amine or three (t-fourth) amine.And, can use the monoalkylamine, two alkylamine, the trialkylamine that comprise alkyl with 5 or more a plurality of carbon atoms, or the alkylamine of replacing, for example ethamine, diethylamide or triethylamine.
With regard to the solubility of alkaline aqueous solution, preferably comprise and have three or still less monoalkylamine or two alkylamine of the alkyl chain of carbon atom, for example, ethamine, dimethylamine or diethylamide.Same reason, the alkylamine with hydrophilic replacement group also is desirable, for example, monoethanolamine, diethanol amine or triethanolamine.
It is solvent or with alcohol or other polar solvents that alkaline aqueous solution is defined as with water, wherein is added with the solution of alkali compounds.The example of alcohol comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, t-butanols, 2-methyl cellosolve, cellosolvo, butoxy ethanol and ethylene glycol.The example of polar solvent comprises acetonitrile, dimethyl formamide, methyl-sulfoxide, N-methylamine pyrrolidones (NMP) and propene carbonate.Basic examples for compounds comprises NaOH, potassium hydroxide, calcium hydroxide and alkali alcoholate.
Have the C4 position and be not substituted basic replacement and C2, C3, C5 and C6 position and be substituted the concentration that base replaces or be not substituted the phenol derivatives that base replaces and be approximately the 0.01-10 mol, preferably the 0.1-2 mol.The concentration of alkylamine is approximately the 0.05-1 mol, preferably the 0.1-0.6 mol.Basic compound concentrations is like this, make the mole of the basic compound comprise be approximately to have the C4 position be not substituted basic replacement and C2, C3, C5 and C6 position be substituted base replace or be not substituted the phenol derivatives that base replaces mole 0.5-2 doubly, preferably 0.5-1.2 is doubly.
As for metallic conductor, can use its component to comprise the metallic conductor of Zn, Sn, Ni, Al, Cr, Fe, Cu, Ti, Ag, Pd, In, Pt, Au or its alloy.The example of best metal conductor comprises that its component comprises the metallic conductor of Cu or its alloy.Herein, the metallic conductor that limits element (for example, Zn, Sn, Ni, Al, Cr, Fe, Cu, Ti, Ag, Pd, In, Pt, Au) its " component comprises " one is meant and comprises one or more metallic compounds comprising the qualification element.
As for the counter electrode that in electrolysis polymerization, uses, can use to comprise one or more by for example electrode of the various materials of iron, stainless steel, Al, Pd, Pt, Au or C.
When reaction equation 1 showed the use metallic conductor as work electrode, the C4 position was not substituted basic replacement and C2, C3, C5 and C6 position are substituted the cell reaction that base replaces or be not substituted the anodic oxidation reactions form appearance of the basic phenol derivatives that replaces to have.Specifically, this reaction is to exist benzene oxygen radical ion under the alkaline aqueous solution situation to develop into the oxidizing process of benzene oxygen radical.
(reaction equation 1)
Herein, X
2, X
3, X
5, X
6Expression is as mentioned above at the hydrogen or the substituent of C2, C3, C5 and C6 position respectively.
The electromotive force of work electrode depends on for example reaction condition and the employed alkaline aqueous solution of the chemical constitution of specific phenolic derivative in the electrolysis polymerization reaction, and the C4 position of described phenol derivatives is not substituted basic replacement and C2, C3, C5 and C6 position are substituted the base replacement or are not substituted the base replacement.Although it is also unrestricted to be added in the voltage at electrode two ends, be preferably the 0.5-5 volt.
Begin to a series of reaction that produces a kind of insulating polymer from electrolysis polymerization, be to realize by the match reaction between monomer or the polymer benzene oxygen radical, this match reaction makes the quantity of the repetitive of polymerization reaction increase by one at every turn, shown in following reaction equation 2.In the process of reaction, can generate a kind of coating of electric insulation, and anode (for example work electrode) can lose activity, the electric current in the electrolytic process is reduced at leisure, stop until polymerization reaction, also stop to generate coating thus.
Though generating the technology of this coating structure by the reaction of phenol derivatives electrolysis polymerization is known as usual, but known method only can generate the coating (doing with copper under the condition of electrode) of about 0.1 micron thickness, is stopping reaction than reflecting point early relatively because generate the reaction meeting of coating.On the contrary, because the existence of alkylamine is arranged in alkaline aqueous solution, method provided by the invention can generate about 0.5 micron polymer coating, and more excellent is to generate about 2 microns or thicker coating.
Second aspect of the present invention provided a kind of method that generates polymer coating, and this method may further comprise the steps: a kind of metallic conductor is immersed in a kind of alkaline aqueous solution that contains phenol derivatives, polymerization single polymerization monomer and alkylamine.The C4 position of phenol derivatives described here is not substituted basic replacement and C2, C3, C5 and C6 position and is substituted base and replaces or be not substituted; Polymerisable monomer described here contains a unsaturated C-C key.Make electrode with metallic conductor then, make phenol derivatives and contain a unsaturated C-C key polymerisable monomer generation electrolysis polymerization reaction.Hereinafter will narrate this method.
Because have the C4 position not to be substituted that basic replacement and C2, C3, C5 and C6 position are substituted that base replaces or unsubstituted phenol derivatives, contain the existence of the polymerisable monomer and the alkylamine of a unsaturated C-C key, make phenol oxygen radical that electrolysis produces influence the polymerization reaction that free radical adds simultaneously and become possibility as starting the factor.Like this, the polymerisable monomer of a phenol derivatives and a unsaturated C-C key can form thicker polymer plating layer on the surface of metallic conductor electrode as polymers compositions.
It is any that soluble polymerisable monomer can be as the polymerisable monomer that the polymerization reaction of a unsaturated C-C key is arranged in alkaline solution.The described polymerisable monomer that contains unsaturated C-C key for example, include but not limited to the polymerisable monomer that contains unsaturated C-C key enumerated below: acrylamide, Methacrylamide, hydroxyalkyl acrylates (for example hydroxy ethyl methacrylate), hydroxyalkyl methacrylates (for example hydroxyl second methacrylate), acrylic acid, methacrylic acid, methylallyl alcohol, PAG (two) acrylate (for example polyethylene glycol (two) acrylate), PAG (two) methacrylate (for example polyethylene glycol (two) methacrylate), di alkylamino group alkane methacrylate, acryloyl alkoxyl trialkyl ammonium chlorine or methacryl alkoxyl trialkyl ammonium chlorine. the concentration range of polymerization single polymerization monomer in alkaline solution that contains unsaturated C-C key is greatly about 0.01 to 10 mol, and more preferably scope is approximately 0.1 to 2 mol.
A second aspect of the present invention can be with the method realization same with first aspect.
A third aspect of the present invention has provided a kind of method that generates polymer coating, and this method may further comprise the steps: a kind of metallic conductor is immersed a kind of containing in the phenol derivatives alkaline aqueous solution.The C4 position of the phenol derivatives here is not substituted the substituted radical that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position and replaces.Make electrode with metal then, make the reaction of phenol derivatives generation electrolysis polymerization.Hereinafter will narrate this method.
In the embodiments of the invention, the unsaturated C-C key substituted radical that has that the C4 position is not substituted the phenol derivatives of the substituted radical selectivity replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position includes but not limited to following substituted radical: unsaturated aliphatic hydrocarbon or aromatic hydrocarbon group such as vinyl groups, the acrylic group, propargyl group or allene base group, any other group that contains unsaturated C-C key can both be suitable for.
In the embodiments of the invention; other substituted radicals in the substituted radical of phenol derivatives except that the substituted radical that contains a unsaturated C-C key at least include but not limited to following substituted radical: the aliphatic hydrocarbon group of the unsaturated or saturated 1-12 of having carbon atom or the aromatic hydrocarbon group of 6-12 carbon atom is arranged; alkoxy grp; amino group; carboxyl groups; alkoxycarbonyl groups, amide group.
Described C4 position is not substituted in the phenol derivatives of the substituted radical replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position, following phenol derivatives can preferably be suitable for: the 2-chavicol, and its C6 position is substituted or is not substituted; 2-(1-acrylic) phenol, its C6 position is substituted or is not substituted; The 2-phenol ethylene, its C6 position is substituted or is not substituted; The 3-chavicol, its C6 position is substituted or is not substituted.
Described C4 position is not substituted the concentration range of phenol derivatives in alkaline solution of the substituted radical replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position greatly about 0.01 to 10 mol, more preferably scope is approximately 0.1 to 2 mol. and the mole of the component of alkaline aqueous solution neutral and alkali compound is about 0.5 to 2 times of mole of phenol derivatives, is preferably 0.5 to 1.2 times.
The reaction equation of cell reaction is shown in following equation 3 and equation 4.Shown in equation 3, the phenol derivatives that the C4 position is not substituted the substituted radical replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position is converted into the phenoxy group ion, generates the phenoxy group free radical by oxidation reaction again.Next step of reaction, shown in equation 4, the aromatic rings of benzene oxygen radical and phenol derivatives reaction, or and the aromatic rings reaction of the polymer that produces, or react with unsaturated C-C key in the substituted radical.Like this, this polymerization reaction can go on.
Be not substituted the electrolysis polymerization reaction of the phenol derivatives of the substituted radical selectivity replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position by the C4 position, add the reaction that contains the substituted radical of unsaturated C-C key with at least one, can generate a kind of product of cross-linked structure.And, even electrolyte makes the product of polymerization reaction expand and becomes gel. and in the later stage of polymerization reaction, expansion can also make electrolyte arrive near the electrode, and makes cell reaction to continue longer a period of time incessantly.Like this, the present invention can provide a kind of insulating blanket of tens micron thickness, and this is that conventional electrolysis polymerization reaction method is inaccessiable.
(reaction equation 3)
(reaction equation 4)
Here, R1, R2 and R3 can be respectively methyl or hydrogen base, Xn represents to contain the remainder of the substituted radical of a unsaturated C-C key, represents not contain the substituted radical of unsaturated C-C key when Xm is arranged, and also has, P and q represent number of repeat unit separately, the integer as from 1 to 100.
Though the present invention does not limit interelectrode magnitude of voltage, for instance, be used in interelectrode voltage preferable range between about 0.5 to 5 volt.
A fourth aspect of the present invention has provided a kind of method that generates polymer coating, and this method may further comprise the steps: a kind of metallic conductor is immersed in a kind of alkaline aqueous solution that contains phenol derivatives and polymerisable monomer.The C4 position of the phenol derivatives here is not substituted the substituted radical selectivity that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position and replaces.Make electrode with metal then, make the reaction of phenol derivatives and polymerisable monomer generation electrolysis polymerization.Hereinafter will narrate this method.
Because the existence of polymerisable monomer in the alkaline aqueous solution of the phenol derivatives that the substituted radical selectivity that has the C4 position not to be substituted to have at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position replaces, polymerisable monomer and phenol derivatives are inequality, make the copolyreaction of carrying out free radical simultaneously as the reaction startup factor with ionization generation phenoxy group free radical become possibility, therefore can form the structure and the physicochemical properties of different insulating blankets.
In the embodiments of the invention, be not substituted the polymerisable monomer that phenol derivatives that the substituted radical that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position replaces coexists as in the alkaline aqueous solution with the C4 position and include but not limited to following polymerisable monomer: the C4 position is not substituted that basic replacement and C2, C3, C5 and C6 position are substituted that base replaces or unsubstituted phenol derivatives (do not comprise contain in the substituted radical a unsaturated C-C key phenol derivatives), and polymerisable monomer has a unsaturated C-C key.
In the embodiments of the invention; described C4 position is not substituted basic replacement and C2, C3, C5 and C6 position and is substituted that base replaces or the substituted radical of C2, C3, C5 and the C6 position of unsubstituted phenol derivatives includes but not limited to following group: the unsaturated or saturated 1-12 of having carbon atom; be preferably the aliphatic hydrocarbon group of 1-7 carbon atom or the aryl radical group of 6-12 carbon atom is arranged; alkoxy base; the alkoxyalkyl group; carboxyl groups; alkoxycarbonyl groups; the amide groups group; the carbamyl alkyl group, hydroxyalkyl group.
It is any that soluble polymerisable monomer can both be as the polymerisable monomer that a unsaturated C-C key is arranged in alkaline solution.The polymerisable monomer that contains unsaturated C-C key for example, be not subjected to any restriction, comprise the polymerisable monomer that contains unsaturated C-C key that is not limited to enumerate below: acrylamide, Methacrylamide, hydroxyalkyl acrylates (for example hydroxy ethyl methacrylate), hydroxyalkyl methacrylates (for example hydroxyl second methacrylate), acrylic acid, methacrylic acid, methylallyl alcohol, PAG (two) acrylate (for example polyethylene glycol (two) acrylate), PAG (two) methacrylate (for example polyethylene glycol (two) methacrylate), di alkylamino group alkane methacrylate, acryloyl alkoxyl trialkyl ammonium chlorine or methacryl alkoxyl trialkyl ammonium chlorine. the concentration range of polymerisable monomer in alkaline solution that contains unsaturated C-C key is greatly about 0.01 to 10 mol, and more preferably scope is approximately 0.1 to 2 mol.
A fourth aspect of the present invention can be with the method realization same with first aspect.
In one embodiment of the invention, contain the phenol derivatives that alkylamine and C4 recited above position are not substituted the substituted radical replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position in the alkaline solution.Narrate this feature of the present invention now.
Because contain the phenol derivatives that alkylamine and C4 recited above position are not substituted the substituted radical replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position in the alkaline solution, may be to be activated by alkylamine, can generate a kind of thicker insulation polymer plating layer like this as the metal surface of electrode.
Be not substituted basic replacement and C2, C3, C5 and C6 position in the C4 position and be substituted under the condition that base replaces or unsubstituted phenol derivatives exists, soluble alkyl amine can both be suitable in alkaline solution (making electrolyte).The alkylamine concentration range is greatly about 0.01 to 1 mol in alkaline solution, and more preferably scope is approximately 0.1 to 0.6 mol.
In another embodiment of the present invention, the phenol derivatives that the C4 position is not substituted the substituted radical replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position can be the 2-chavicol, 2-(1-acrylic) phenol or 2-pi-allyl-6-methylphenol.Narrate this feature of the present invention now.
The phenol derivatives that C4 position in the certain preferred embodiments of the invention is not substituted the substituted radical replacement that has at least a position to be contained a unsaturated C-C key at least in basic replacement and C2, C3, C5 and the C6 position comprises the 2-chavicol, 2-(1-acrylic) phenol or 2-pi-allyl-6-methylphenol.The reaction of the electrolysis polymerization reaction by this phenol derivatives and the unsaturated C-C key of substituted radical can generate a kind of product with better cross-linked structure.Discussion had been carried out in the effect of this cross-linked structure in the above.
In another embodiment of the present invention, the metallic conductor that uses in above-mentioned electrolysis polymerization reaction can be a kind of material of the Cu of comprising component.Now just this feature of the present invention is described.
As everyone knows; by using ethylenediamine; can form the polymer coating that a kind of thickness reaches 10 μ m; this is using phenol and as the o-chlorphenol of phenol derivatives, and to use in the electrolysis polymerization scheme of Fe as the metallic conductor of electrode be very basic (F.Bruno, M.C.Pham; and J.E.Dubois; Electrochimica Acta, 22,451-457 (1977)).However, if use Cu can generate a kind of complex compound as ethylenediamine copper as the electrode metal conductor in this scheme, like this, the Cu electrode just can obtain overflowing.Therefore, it is very difficult stably forming a kind of polymer coating at the Cu electrode surface.
On the contrary, the method according to this invention, by add alkylamine in alkaline aqueous solution, this material can prevent the dissolving of Cu electrode, can form a kind of thickness and be approximately 0.5 μ m or thicker polymer coating.
The metallic conductor that comprises the Cu component includes but not limited to following material: cathode copper, deoxidized cooper, oxygen-free copper, brass (comprising Zn) does not have processing brass (comprising Zn and Pb), admirality brass (comprising Zn and Sn), bronze (comprising Sn and P), aluminium bronze (comprising Al), Corson alloy (comprising Ni and Si), Heusler alloy (comprising Mn and Al), German silver (comprising Zn and Ni), corronil (comprising Ni), beryllium copper, ambrose alloy, silver-bearing copper, cadmium copper and chromium-copper.
Method of the present invention is particularly useful for forming on the surface of the metallic conductor that comprises the Cu component a kind of insulating polymer coating, and by roll-in or roll-in and cutting, is processed into the element that a kind of cross section is a rectangle.
Usually the method that forms polymer coating on the element of square-section is to use a kind of insulating varnish on metallic conductor, there is following problem in its oven dry, because it is lack than the quantity on the bigger flat horizontal surface of area, relatively poor in the insulating properties of the polymer coating of end face at lacquer sticking on the element end face; The common solution of this problem is the quantity that is increased in the lacquer of end face, and this just requires to be increased in the quantity of the lacquer on the bigger flat horizontal surface of area inevitably.On the contrary, adopt method of the present invention to make and also form sufficient polymer coating on the end face of metallic conductor element.
In one embodiment of the invention, adopt the electrolysis polymerization thing of above-mentioned any method preparation can comprise a step again, metallic conductor (its surface has polymer coating) is immersed in the water, or other aqueous solution except above-mentioned alkaline aqueous solution, or a kind of alcoholic solution.Now just this feature of the present invention is described.
In some embodiments of the invention of electrolysis polymerization thing, when using a kind of phenol derivatives, not being substituted base as a kind of C4 position replaces, C2, C3, C5 and C6 position are substituted the phenol derivatives that base replaces or be not substituted the base replacement, and the polymer coating of finishing the reacted generation of electrolysis polymerization may expand owing to making electrolytic solution with alkaline aqueous solution.Under these circumstances, the electrolyte in the electrolytic solution may be retained in the polymer coating, thereby reduces its insulating capacity.Can metallic conductor (its surface has polymer coating) be immersed in the water by adopting, or other aqueous solution except above-mentioned alkaline aqueous solution, or the way in a kind of alcoholic solution, remove these electrolyte in the polymer coating of generation, thereby improve the insulating capacity of polymer coating greatly.
The liquid that uses in this infiltration step can be water, or the aqueous solution or the alcoholic solution of any polymer coating that can the dissolution of metals conductive surface form.The suitable aqueous solution includes, for example, and the acidic aqueous solution (for example, hydrochloric acid, sulfuric acid, nitric acid, or acetic acid) and slaine (for example, sodium chloride or the potassium chloride) aqueous solution.Suitable alcoholic solution comprises those, if necessary, acid and/or slaine and/or other compounds is dissolved in the solution that is prepared from alcohol (for example, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, t-butanols, or the ethylene glycol) solvent.
Also possible, after finishing the electrolysis polymerization reaction, except carrying out above-mentioned infiltration step or replace above-mentioned infiltration step, add at metallic conductor with between electrode one with the electrolysis polymerization course of reaction in the different electric field of polarity that uses, to strengthen absorption to ion residual in the polymer coating.
In another embodiment of the present invention, adopt the electrolysis polymerization thing of above-mentioned any method preparation can comprise a step again, the polymer coating that obtains in the electrolysis polymerization reaction is heated.Now just this feature of the present invention is described.
After finishing the electrolysis polymerization reaction, by heated polymerizable thing coating, the pressure in the polymer coating is weakened, and like this, just can obtain the coating good with the adhesion of metallic conductor.Better scheme is, polymer coating is heated to the temperature of the softening point that is equal to or higher than the polymer of forming polymer coating, like this, just can obtain the polymer coating that electrical insulating property is further improved.Optimum condition is to be higher than the polymer softening point in temperature to heat 1 to 30 minute down for 10 to 100 ℃.
Especially, have one in use and be not substituted the C4 position that base replaces, and C2, C3, have at least one to replace the position in C5 and the C6 position, and at least one substituting group has under the situation of phenol derivatives of a undersaturated C-C key, can think, this heating can strengthen the reaction between any unsaturated C-C key that is retained in the polymer coating, thereby coating forms a more fine and close cross-linked structure.Therefore, can obtain the polymer coating that intensity increases.
If carry out above-mentioned infiltration step, heating steps carries out after then being preferably in and soaking into step.
In another embodiment of the present invention, metallic conductor is coated with one deck electric insulation coating, and wherein, insulating blanket comprises a defective part.
Here said " being coated with the metallic conductor of one deck electric insulation coating " is meant an enamelled wire, and its surface covers an insulating barrier by using lacquer or similar substance, or a metallic conductor, and its surface coverage has oxide or similar substance.If these insulating blankets comprise a defective part, for example, the part that an insulating properties is relatively poor is conducted electricity in this defective part branch.By being electrode with the defect part, metallic conductor immersed in a kind of alkaline aqueous solution that includes above-mentioned phenol derivatives carry out the electrolysis polymerization reaction, can form a polymer coating with as insulating blanket at defect part.The method of the application of the invention can be recovered defective insulating barrier lead at an easy rate selectively, or the insulation characterisitic of electronic device such as transformer conductor or electric capacity for example.
In a fifth aspect of the present invention, provide a kind of metallic conductor that has the polymer insulation coating that forms by said method on it.Below, just this method is described.
According to the method for above-mentioned production polymer coating, can be at lead, or analog, on metallic conductor, form thickness at submicron order, approximately to the polymer coating of 10 μ m or 100 μ m.
Especially, the lead of the tape insulation coating of Xing Chenging by this method, its thickness of coating is less than the coating that forms by the method for using lacquer and oven dry.When adopting the insulating barrier lead that forms by this method, can obtain higher winding density by per unit volume, thereby can improve the efficient of motor as the winding conducting wire of motor.
By using a kind of polymer coating based on electrolysis polymerization reaction as shown in Figure 1 to generate equipment, the method for production polymer coating of the present invention can be used on the one dimension object, for example on electric lead.
As shown in Figure 1, lead 3 on wheel 1 can immerse by pulley 7 and taking-up from electrolysis tank 2, fill electrolyte 5 in the electrolysis tank 2, this electrolyte 5 is a kind of phenol derivatives that contain, but have the polymerisable monomer of a unsaturated C-C key and the alkaline aqueous solution of aforesaid a kind of alkylamine.
By will to electrode 4 be placed on one not can with moving lead 3 position contacting, and power supply 6 is connected to electrode 4 and pulley electrode 7 (being electrically connected with lead 3), the electrolysis polymerization reaction can be finished in electrolysis tank 2.As required, can also use rinse bath 8 and/or a drying oven 10 of filling a kind of cleaning solution 9 (for example any in the water or the above-mentioned aqueous solution) to carry out the electrolysis reprocessing.The lead that is fit to this processing method can be by on wheel 11, so that a kind of lead that has polymer coating to be provided.Further, can also before carrying out the electrolysis polymerization reaction, clean and/or corrosion treatment as required, to remove the oil or the oxide-film on metallic conductor surface.
Below, will the present invention be described in more detail by example, still, scope of the present invention is not limited to these examples.
(example 1)
Containing 2 of 0.5mol/l, the 6-dimethylphenol, 0.2mol/l diethylamide and the alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) of the potassium hydroxide of 0.5mol/l.Making alive makes the voltage of Cu electrode with respect to an Ag/AgCl reference electrode maintenance 0.5V, and the electrolysis polymerization reaction was carried out 1.5 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 1.8 μ m.
The Cu electrode that a plurality of such parts are coated with insulating polymer coating gathers into folds and does a mutual conduction test, and the insulation that the result demonstrates between the folded mutually Cu electrode is gratifying.
(example 2)
It is the burin-in process of carrying out in 220 ℃ the thermostat 5 minutes that the Cu electrode of a tape insulation polymer coating of making according to the method for example 1 is placed on a temperature.Next step by vapor deposition, forms an aluminium lamination on polymer coating.Electric insulation between the exposed part of aluminium lamination and Cu electrode (that is, not covering the part of above-mentioned polymer coating) is measured as 1.5 * 10
14Ω cm.
(example 3)
Containing the phenol of 0.5mol/l, 0.2mol/l hydroxyethyl methacrylate, 0.2mol/l triethylamine, alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) with the potassium hydroxide of 0.5mol/l.Making alive makes the voltage of Cu electrode with respect to an Ag/AgCl reference electrode maintenance 0.8V, and the electrolysis polymerization reaction was carried out 1.5 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 2.7 μ m.
The Cu electrode that a plurality of such parts are coated with insulating polymer coating gathers into folds and does a mutual conduction test, and the insulation that the result demonstrates between the folded mutually Cu electrode is gratifying.
(example 4)
It is the burin-in process of carrying out in 150 ℃ the constant temperature bath 5 minutes that the Cu electrode of a tape insulation polymer coating of making according to the method for example 3 is placed on a temperature.Next step by vapor deposition, forms an aluminium lamination on polymer coating.Electric insulation between the exposed part of aluminium lamination and Cu electrode (that is, not covering the part of above-mentioned polymer coating) is measured as 2 * 10
13Ω cm.
(example 5)
Alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) at the potassium hydroxide of 2-chavicol that contains 0.7mol/l and 0.7mol/l.Between Cu electrode (anode) and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 0.3 μ m.
(example 6)
Containing the 2-chavicol of 0.7mol/l, 0.3mol/l diethylamide and the alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) of the potassium hydroxide of 0.7mol/l.Between Cu electrode (anode) and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 34 μ m.
(example 7)
Containing the 2-chavicol of 0.7mol/l, 0.3mol/l triethylamine and the alkaline aqueous solution (water: ethanol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) of the potassium hydroxide of 0.7mol/l.Between Cu electrode (anode) and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 5 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 10 μ m.
(example 8)
Containing the 2-of 0.7mol/l (1-acrylic) phenol, 0.3mol/l diethylamide and the alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) of the potassium hydroxide of 0.7mol/l.Between Cu electrode (anode) and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 25 μ m.
(example 9)
Containing the 2-chavicol of 0.7mol/l, 0.3mol/l diethylamide and the alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) of the potassium hydroxide of 0.7mol/l.Between Cu electrode (anode) and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 30 μ m.
(example 10)
Containing the 2-chavicol of 0.7mol/l, 0.7mol/l 2, the 6-xylenol, 0.6mol/l diethylamide and the alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) of the potassium hydroxide of 1.4mol/l.Between Cu electrode (anode) and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 30 μ m.
(example 11)
Containing the 2-chavicol of 0.7mol/l, 0.7mol/l phenol, 0.6mol/l diethylamide and the alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm) of the potassium hydroxide of 1.4mol/l.Between Cu electrode (anode) and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 52 μ m.
(example 12)
By using the polymer coating based on the electrolysis polymerization reaction as shown in Figure 1 to generate equipment, polymer coating is at copper cash (diameter: generate continuously 0.1mm).The solution that uses in the electrolysis tank 2 is to contain 2 of 0.5mol/l, 6-xylenol, the hydroxyethyl methacrylate of 0.1mol/l, the alkaline aqueous solution of the diethylamide of 0.2mol/l and the potassium hydroxide of 0.5mol/l (water: methyl alcohol=75: 25 percents by volume).Electrolysis polymerization is reflected under the condition of Cu lead electrode with respect to the voltage of an Ag/AgCl reference electrode maintenance 0.6V and carries out, and the Cu lead electrode passes electrolysis tank 2 (length: 10m), move with the linear velocity of 0.2 meter per second.Generated a coil that is made of the Cu line of tape insulation polymer coating, this coil has gratifying coating strength and insulating properties like this.
(example 13)
On a Cu lead that has the square-section that forms by roll-in of copper base and cutting, the oven dry then of plating lacquer, like this, the average thickness of the painting on surface that the area of Cu lead is bigger is approximately 0.7 μ m.Because only there is very a spot of lacquer to stick on the end face of Cu lead, can see having some not covered thereby uninsulated defect part by lacquer.By making the polymer coating based on the electrolysis polymerization reaction in the use-case 12 generate equipment, the insulation defect part is covered with polymer coating selectively.Therefore, the insulation defect of the end face of Cu lead is eliminated.
(example 14)
Enamelled wire (diameter: 1mm) be wound into the coil of a diameter 2cm, and part lacquer coating ground off with sand paper, thereby have on-insulated electrode.Containing the 2-chavicol of 0.7mol/l, 0.3mol/l the alkaline aqueous solution of the potassium hydroxide of diethylamide and 0.7mol/l (water: methyl alcohol=75: 25 percents by volume), immerse enamelled wire and a Pt to electrode (being the bonding jumper of 5 * 60 * 0.1mm).Between Cu electrode and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, remove the Cu electrode from solution, the part that the lacquer coating on the Cu electrode is ground off has optionally generated insulating blanket.After the electrolysis polymerization reaction, will carry out interelectrode conductive test in enamelled wire and the Pt electrode immersion salting liquid, the result shows that insulating properties is very good.
(example 15)
Enamelled wire (diameter: 1mm) be wound into the coil of a diameter 2cm, and part lacquer coating ground off with sand paper, thereby have on-insulated electrode.Containing the 2-chavicol of 0.7mol/l, 0.7mol/l phenol, 0.6mol/l the alkaline aqueous solution of the potassium hydroxide of diethylamide and 1.4mol/l (water: methyl alcohol=75: 25 percents by volume), in the enamelled wire (part is coated with lacquer coating and ground off) and a Pt counter electrode (being the bonding jumper of 5 * 60 * 0.1mm) immersion solution with example 14.Between Cu electrode and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, remove the Cu electrode from solution, the part that the lacquer coating on the Cu electrode is ground off has optionally generated insulating blanket.After the electrolysis polymerization reaction, will carry out interelectrode conductive test in enamelled wire and the Pt electrode immersion salting liquid, the result shows that insulating properties is very good.
(example 16)
A fan motor is used as the draft fan of vehicle, according to example 16 enamelled wire that has insulation defect is carried out the electrolysis polymerization reaction as electrode.Containing the 2-chavicol of 0.7mol/l, 0.3mol/l diethylamide and the alkaline aqueous solution (water: methyl alcohol=75: 25 percents by volume), a motor and a Pt counter electrode (being the bonding jumper of 5 * 60 * 0.1mm) are immersed in the solution of the potassium hydroxide of 0.7mol/l.Between Cu electrode and Pt electrode, add 3V voltage, the electrolysis polymerization reaction was carried out 20 minutes.Then, remove motor from solution, the result shows that insulating blanket successfully optionally generates on the insulation defect of coil of conductive wire part.To contain the nonwoven fabrics that the solution immersion of sodium chloride and phenolphthalein crosses and be placed on this motor, and add voltage, like this, motor is a negative electrode.But phenolphthalein does not occur painted because of producing hydrogen.Therefore, can be sure of that the insulating blanket that generates according to this example has extraordinary insulating properties.
(Comparative Examples 1)
Containing 2 of 0.5mol/l, the alkaline aqueous solution of the potassium hydroxide of 6-xylenol and 0.5mol/l (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm).Making alive makes the voltage of Cu electrode with respect to an Ag/AgCl reference electrode maintenance 0.5V, and the electrolysis polymerization reaction was carried out 1.5 minutes.Then, from solution, remove the Cu electrode, fully clean, and dry.According to weight, the thickness that measures the polymer coating that forms on the electrode is 0.1 μ m.
The Cu electrode that a plurality of such parts are coated with insulating polymer coating gathers into folds and does a mutual conduction test, and the result demonstrates between the folded mutually Cu electrode on-insulated basically.
(Comparative Examples 2)
Containing the phenol of 0.5mol/l, the alkaline aqueous solution of the diethylamide of 0.2mol/l and the potassium hydroxide of 0.5mol/l (water: methyl alcohol=75: 25 percents by volume), immerse a Cu electrode and a Pt electrode (being the bonding jumper of 5 * 60 * 0.1mm).Making alive makes the voltage of Cu electrode with respect to an Ag/AgCl reference electrode maintenance 0.5V, and the electrolysis polymerization reaction is carried out.Purple solution has appearred from the Cu electrode.Then, remove the Cu electrode from solution, the Cu electrode that obtains is corroded.Go out the Cu electrode from this results presumption and overflowed, thereby generated the diethylamide copper solution.
According to the present invention, can on metallic conductor, generate very thin insulating blanket securely.Further, can on the such metallic conductor of copper, generate insulating blanket, and be unusual difficulty with conventional electrolysis polymerization reaction method.Further again, according to the present invention, the insulation defect that is coated with the metallic conductor of insulating blanket can be easy to repair.The present invention can be used for producing the lead that has thin insulating coating.These leads can be used for realizing microminiaturized, and the performance of intensifier coil, and the insulation defect of repairing coil.
Within the scope of the present invention, according to spirit of the present invention, those of ordinary skill in the art can make improvements at an easy rate.Therefore, below the scope of appended claim be not limited to the specification of front, but can do wideer explanation.
Claims (15)
1. a method that produces polymer plating layer is characterized in that, comprises following steps:
Metallic conductor is immersed in the alkaline aqueous solution, and described alkaline aqueous solution comprises and is selected from phenol, 2, the phenol derivatives and the alkylamine of 6-xylenol, 2-chavicol, 2-(1-acrylic) phenol, 2-pi-allyl-6-methylphenol or its combination in any; And
Carry out electrolysis polymerization with metallic conductor as the electrode pair phenol derivatives.
2. the method for generation polymer plating layer according to claim 1 is characterized in that, described metallic conductor is the metallic conductor that its component comprises copper.
3. the method for generation polymer plating layer according to claim 1 is characterized in that, and is further comprising the steps of after described electrolysis polymerization step: the metallic conductor that is formed with polymer plating layer on it is immersed in water or any non-alkaline aqueous solution or the alcoholic solution.
4. the method for generation polymer plating layer according to claim 1 is characterized in that, also comprises the step that the polymer plating layer that is produced by electrolysis polymerization is heated after described electrolysis polymerization step.
5. the method for generation polymer plating layer according to claim 1 is characterized in that, described metallic conductor is coated with the electrolysis insulating barrier, and this insulating blanket comprises defect part.
6. a method that produces polymer plating layer is characterized in that, may further comprise the steps:
Metallic conductor is immersed in the alkaline aqueous solution, described alkaline aqueous solution comprises and is selected from phenol, 2,6-xylenol, 2-chavicol, 2-(1-acrylic) phenol, 2-pi-allyl-6-methylphenol or the phenol derivatives of its combination in any, the polymerisable monomer with unsaturated C-C key and alkylamine; And
With metallic conductor as the electrode pair phenol derivatives with have unsaturated C-C key polymerisable monomer and carry out electrolysis polymerization.
7. the method for generation polymer plating layer according to claim 6 is characterized in that, described metallic conductor is the metallic conductor that its component comprises copper.
8. a method that produces polymer plating layer is characterized in that, may further comprise the steps:
Metallic conductor is immersed in the alkaline aqueous solution, and described alkaline aqueous solution comprises the phenol derivatives that is selected from 2-chavicol, 2-(1-acrylic) phenol and 2-pi-allyl-6-methylphenol; And
Carry out electrolysis polymerization with metallic conductor as the electrode pair phenol derivatives.
9. the method for generation polymer plating layer according to claim 8 is characterized in that, described alkaline aqueous solution also comprises alkylamine.
10. a kind of method that produces polymer plating layer according to claim 8 is characterized in that described metallic conductor is the metallic conductor that its component comprises copper.
11. a kind of method that produces polymer plating layer according to claim 8, it is characterized in that further comprising the steps of after described electrolysis polymerization step: the metallic conductor that is formed with polymer plating layer on it is immersed in water or any non-alkaline aqueous solution or the alcoholic solution.
12. the method for generation polymer plating layer according to claim 8 is characterized in that, also comprises the step that the polymer plating layer that is produced by electrolysis polymerization is heated after described electrolysis polymerization step.
13. the method for generation polymer plating layer according to claim 8 is characterized in that, described metallic conductor plating has the electrolysis insulating blanket, and this insulating blanket comprises defect part.
14. the metallic conductor of a tape insulation coating is characterized in that comprising:
Metallic conductor, and
The polymer coating that on the part or all of surface of metallic conductor, forms by the described method of claim 1.
15. the metallic conductor of a tape insulation coating is characterized in that comprising:
Metallic conductor, and
The polymer coating that on the part or all of surface of metallic conductor, forms according to the described method of claim 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9432398 | 1998-04-07 | ||
| JP(10)094323 | 1998-04-07 | ||
| JP094323/1998 | 1998-04-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231486A CN1231486A (en) | 1999-10-13 |
| CN1291421C true CN1291421C (en) | 2006-12-20 |
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ID=14107086
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991054709A Expired - Fee Related CN1291421C (en) | 1998-04-07 | 1999-04-07 | Method for forming polymer plating layer and metal conductor with isolation plating layer |
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| Country | Link |
|---|---|
| JP (1) | JP4334663B2 (en) |
| KR (1) | KR100349794B1 (en) |
| CN (1) | CN1291421C (en) |
| MY (1) | MY121055A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7200060B2 (en) * | 2018-07-17 | 2023-01-06 | 太陽ホールディングス株式会社 | Polyphenylene ethers, curable compositions containing polyphenylene ethers, dry films, prepregs, cured products, laminates, and electronic components |
| KR20210032387A (en) | 2018-07-17 | 2021-03-24 | 다이요 홀딩스 가부시키가이샤 | Polyphenylene ether, curable composition containing polyphenylene ether, dry film, prepreg, cured product, laminate, and electronic parts |
| JP7418985B2 (en) * | 2018-09-28 | 2024-01-22 | 太陽ホールディングス株式会社 | Curable compositions, dry films, cured products, and electronic components |
| JP7369581B2 (en) * | 2019-09-30 | 2023-10-26 | 太陽ホールディングス株式会社 | Curable compositions containing polyphenylene ether, dry films, prepregs, cured products, laminates, and electronic components |
| JP2023037449A (en) * | 2021-09-03 | 2023-03-15 | 太陽ホールディングス株式会社 | Photosensitive composition, dry film, cured article, and electronic component |
| CN119070202B (en) * | 2024-11-05 | 2025-02-14 | 江苏创仕澜传输科技有限公司 | Flexible interconnection flat cable bending insulation repair process |
-
1999
- 1999-04-07 CN CNB991054709A patent/CN1291421C/en not_active Expired - Fee Related
- 1999-04-07 MY MYPI99001339A patent/MY121055A/en unknown
- 1999-04-07 JP JP10070399A patent/JP4334663B2/en not_active Expired - Fee Related
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| MY121055A (en) | 2005-12-30 |
| KR100349794B1 (en) | 2002-08-22 |
| JP4334663B2 (en) | 2009-09-30 |
| JP2000104014A (en) | 2000-04-11 |
| CN1231486A (en) | 1999-10-13 |
| KR19990083015A (en) | 1999-11-25 |
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