CA1298567C - Method for making metallic patterns - Google Patents
Method for making metallic patternsInfo
- Publication number
- CA1298567C CA1298567C CA000539829A CA539829A CA1298567C CA 1298567 C CA1298567 C CA 1298567C CA 000539829 A CA000539829 A CA 000539829A CA 539829 A CA539829 A CA 539829A CA 1298567 C CA1298567 C CA 1298567C
- Authority
- CA
- Canada
- Prior art keywords
- resin
- pts
- copper
- photoresist
- electrodeposited
- 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 - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0562—Details of resist
- H05K2203/0582—Coating by resist, i.e. resist used as mask for application of insulating coating or of second resist
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0783—Using solvent, e.g. for cleaning; Regulating solvent content of pastes or coatings for adjusting the viscosity
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
- H05K2203/1333—Deposition techniques, e.g. coating
- H05K2203/135—Electrophoretic deposition of insulating material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/49155—Manufacturing circuit on or in base
Abstract
3-15959/+/ARL 371 Method for making metallic patterns Abstract of Disclosure The present invention provides a method for making a metallic pattern on a substrate having a surface comprising bare metal in predetermined areas and metal coated by a resist in remaining areas which comprises (i) protecting the bare metal by electrodepositing a resin thereon, (ii) while leaving the electrodeposited resin substantially uncured, removing the resist from said remaining areas using a solvent which will not remove the electrodeposited resin, thereby exposing metal in said remaining areas, (iii) etching the metal exposed in (ii) using an etchant which does not remove the electrodeposited resin, and (iv) removing the electrodeposited resin with a suitable solvent.
Description
5~7 3-l5959/+1ARL 371 Method for making metallic patterns The present invention relates to a me~hod for making metalllc patterns such as printed circuits and the like.
There are numerous methods used for the manufacture of printed circ~it boards, although some of the steps used are common to the various methods.
In the case of single sided printed circuit boards, the board, comprising a copper clad base laminate, has holes drilled where desired, a resist i8 coated on the copper in a predetermined pattern, uslng screen printing or photolmaging techniques, to give a board having bare copper in some areas and copper coated by the resist in remaining areas, the bare copper is then plated with a tin-lead alloy, the resist is then removed, the copper thereby exposed is etched USi11g an etchant which does not remove the tin-lead alloy, which i9 finally removed using a tin lead alloy stripper.
In ~the case of double sided, plated through hole printed circuit boards, the procedure is slmilar, but with the following additional steps-after the holes are drilled the board is subjected to electroless copper deposition to deposit copper on the surface of the holes ( as well as over all the copper~and after applying the resist in a ~LZ985~i~
predetermined pattern the board is subjected to copper electroplat-ing to deposit copper on the bare copper parts including the surface of the holes.
Disadvantages of these processes are the high cost of the tin-lead alloy stripper and the necessary subsequent cleaning; and the tin-lead stripper (usually a mixture of hydrogen peroxide and sulphuric acid) is aggressive to the boards themselves and to personnel and equipment used in carrying out the stripping.
Ue have now found that the copper left bare after applying a photoresist can be protected by electrodeposition of an electrode-positable resin that is strippable by a different solvent from that used to strip the photoresist, and which is not removed by the copper etchant.
Electrodepositable resins have been known for many years and are commonly used for coating metal articles e.g. painting car bodies and accessories, steel girders, and household items such as washing machines. In all these uses the resin is electrodeposited and then cured. There has been a proposal in Russian Patent Specification No. 293312 to use an electrodepositable resin to protect exposed copper during the manufacture of a printed circuit board, but again, after electrodeposition the resin is thermally cured. This makes removal dificult and conditions are needed, an alkaline solution at 70 to 80C, which can damage the base laminate of a circuit board.
~e have found that sufficient protection can be given without substantially curing the electrodeposited resin.
Accordingly the present invention provides a method for making a metallic pattern on a substrate having a surface comprising bare metal in predetermined areas and metal coated by a photoresist in remaining areas which comprises (i) protecting the bare metal by electrodepositing a resin thereon, (ii) while leaving the electrodeposited resin substantially uncured, removing the resist ~.'' ~Z9~35;~
21~89-7166 from said remaining areas using a solvent which will not remove the electrodeposited resin, thereby exposing metal in said remaining areas, (iii) etching the metal exposed in (ii) using an etchant which does not remove the electrodeposited resin, and (iv) removing the electrodeposited resin with a suitable solvent.
The photoresist is coated in selected areas by applying it uni-formly to the substrate, which is usually a copper-clad laminate, subjecting it to actinic radiation, in a predetermined pattern and then removing exposed or unexposed areas according to whether the photoresist is positive or negative respectively. Positive and negative photoresists for use in making printed circuit boards are well known materials and any of them may be used. They can be strippable under aqueous conditions or by means of an organic solvent. A layer of another metal such as nickel may be deposited on bare copper areas before electrodeposition of the resin.
The electrodepositable resin may be anodically depositable or cathodically depositable, which are base-strippable and acid-strippable respectively. Anodically depositable resins are preferred if acidic etchants are to be used, and cathodic types are preferred if alkaline etchants for copper are to be used.
A particularly combination is the use of a photoresist which is strippable under aqueous conditions and an electrodepositable resin which is strippable by means of an organic solvent.
Any of the large number of electrodepositable resins may be used including acrylic resins; adducts of epoxide resins with amines or polycarboxylic, amino or mercapto acids; polyurethanes; polyester;
and reaction products of phenolic hydroxyl group-containin~ resins with an aldehyde and amine or amino- or mercapto-carboxylic acids.
Suitable acrylic resins include copolymers of at least one acrylic ester such as an alkyl or hydroxyalkyl acrylate or methacrylate with .~ , ~2~ 7 an ethylenically unsaturated monomer containing a salt-forming group, such as an acrylic monomer containing a carboxyl or tertiary amino group and, optionally, another ethylenically unsaturated monomer. Suitable epoxide resin adducts include those of diglycidyl ethers of dihydric alcohols or bisphenols with a stoichiometric excess of a primary or secondary monoamine or polyamine such as ethanolamine, diethanolamine or ethylenediamlne, a polycarboxylic acid such as glutaric or adipic acid, a polycarboxylic acid anhydride such as maleic or succinic anhydride, an aminocarboxylic acid such as o-, m- or p-aminobenzoic acid or a mercaptocarboxylic acid. Suitable polyurethanes include adducts of hydroxyl-terminated polyurethanes with polycarboxylic acid anhydrides. Suitable polyesters include carboxyl-terminated polyesters derived from polyhydric alcohols such as ethylene glycol, I,2-propylene glycol, 1,3-propylene glycol or butane-1,4-diol with polycarboxylic acids such as glutaric, adipic, maleic, tetrahydrophthalic and phthalic acids or esterlfying derivatives thereof. Suitable reaction products oE phenolic hydroxyl-containing resins include reaction products of phenol-terminated adducts of diglycidyl ethers with bisphenols, aldehydes such as formaldehyde or ben~aldehyde and amines such as ethanolamine, diethanolamlne or ethylene diamine, aminocarboxylic acids such as glycine, sarcosine or aspartic acid, or mercaptocarboxylic acids such as thioglycolic or 3-mercaptopropionic acid.
Preferred electrodepositable resins are copolymers of at least one monoacrylic ester, particularly selected from methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butyl acrylate, ethylhexyl acrylate and the corresponding methacrylates, with at least one monoacrylic monomer containing a carboxyl or tertiary amino group, particularly acrylic acid, methacrylic acid or dimethylaminoethyl methacrylate and, optionally, with a further vinyl monomer such as styrene. Other preferred electrodepositable resins are adducts of a diglycidyl ether of a bisphenol, particularly, bisphenol A, which may have been advanced, with 8 monoamine, particularly diethanolamine.
ilZ9~
The amount of resin deposited needs to be sufficient to cover the exposed metal completely and protect it during removal of the photoresist and during etching of the metal thereby exposed.
Electrodeposition for only a few minutes, usually one minute~ at a voltage of up to 200 volts is sufficient in most cases. Voltages as low as 2 volts may be used in some cases, especially if the size of the electrode on which the resin is deposited is small in relation to the other electrode. For example a cathodically depositable resin may be deposited on a small cathode in a tank where the whole of the tank is the anode, at voltages of 2 volts or 5 volts.
We have found that the adhesion of the coating is improved if it is deposited in two steps, first at a low voltage and then at a slightly higher voltage. For example a good coating can be obtained by electrodepositing the resin at 2 volts for 2 minutes, Eollowed by deposition at S volts for up to 5 minutes.
It is also possible to use a combination of a photoresist and an e].ectrodepositable resin which are both basic or both acidic strippable provided that the photoresist is strippable under milder conditions than are needed to remove the electrodeposited resin, e.g. a more dilute solution of base or acid.
The electrodeposited resin is pre~erably dried without curing it, for example by heating at a temperature up to 100C, before carrying out the etching step (iii), more preferably before removing the resist in step (ii).
When an organic solvent is used to remove the resist, a suitable solvent which does not dissolve the electrodeposited resin can be found by routing experimentation. Both this solvent and ~he solvent used to remove the electrodeposited resin can be selected from halohydrocarbons such as l,l,1-trichloroethane and dichloromethane, hydroxylic solvents such as 2-n-butoxyethanol and 2-ethoxyethanol, i7 esters such as 2-ethoxyethyl acetate, ketones such as acetone and methyl ethyl ketone and ethers such as tetrahydrofuran. Where, for example, the electrodeposited resin is derived from an epoxy resin and the resist is an acrylic material, the resist can be removed using a halohydrocarbon solvent and the electrodeposited resin can be removed USillg a ketone.
The metal exposed by removal of the resist, usually copper, may be removed by any well known etchant such as ferric chloride, hydrogen peroxidelphosphoric acid, ammonium persulphate or cupric chloride.
The present invention is also very useful for use with multilayer circuit boards, especially when via holes and through contacts are present.
The invention is illustrated by the following Examples in which parts are parts by weight. Th0 resins used in the Examples are:
Res1n 1 Methyl methacrylate (55 pts), methacrylic acid (5 pts), 2-hydroxyethyl methacrylate (40 pts) and tsrt.dodecylmercaptan (0.03 pts) are heated to reflux in tetrahydrofuran (THF) ~350 pts).
Azobis(isobutyronitrile) (I.5 pts~ i9 added and the mixture maintained at reflux for 5 hours under nitrogen. The reaction mixture is cooled to ambient temperature and added slowly to stirred hexane (900 pts). A precipitate i9 formed which is filtered off and washed with further hexane. The product is dried at 40C in a vacuum oven to yield 87 pts of a copolymer-acid value 0.56 eqlkg, molecular weight (number average) 7206.
Resin 2 -Styrene (50 pts), dimethylaminoethyl methacrylate (10 pts), ethylhexyl methacrylate (20 pts), 2-hydroxypropyl methacrylate ~20 pts) and tert.dodecylmercaptan (0.03 pts) are dissolved in THF
(340 pts). Azobis(isobutyronitrile) (1.5 pts) in THF (10 pts) is added and the mixture held at re~lux for 5 hours under nitrogen. The :~9~
reaction mixture is stripped under vacuum to obtain a resinous solid which i5 further dried in a vacuum oven at 40C. The solid copolymer obtained has an amine value 0.22 eq/kg and molecular weight (number average) 14,538.
Resin 3 A monomer mixture consisting of styrene (26.25 pts), ethylhexyl acrylate (10 pts), 2-hydroxyethyl methacrylate (10 pts) and dimethylaminoethyl methacrylate (3.75 pts) with azobis(isobutyronitrile) (0.75 pts) is added dropwise over 2 hours to butoxyethanol (25 pts~ stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further hour and further charge of azobis(isobutyronitrile) (0.25 pts) and butoxyethanol (5.0 pts~ added. This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (10 pts) to reduce solids to around 50 % and stripped on a rotary evaporator under vacuum to remove any monomers still present. The amine value of the resulting solution is 0.23 eq/kg and the molecular weight (number average) of the copolymer is 9410.
Resin 4 A monomer mixture consisting of methyl methacrylate (46 pts), butyl acrylate (50 pts), methacrylic acid (~ pts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (25 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (1.5 pts) in butoxyethanol (10 pts) added. This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (20 pts) to reduce solids content to around 50 % and stripped on a rotary ~vaporator under vacuum to removed any monomers still present. The acid value of the resulting solution is 0.23 eq/~g and the molecular weight of the copolymer is 13,276.
~8567 Resin 5 An epoxide resin prepared by advancing a diglycidyl ether of bisphenol A by reaction with bisphenol A (epoxy value 0.99 mol/kg, 100 g) is heated to 140C together with butoxyethanol (60 g) to form a solution. To this is added a solution of diethanolamine (10.7 g) in butoxyethanol (13.8 g) and the temperature of the mixture maintained at 140C for a further 4 hours, after which tims it is cooled. The resulting solution has an amine value of O.S5 mol/kg and an epoxy value of zero.
Resin 6 A monomer mixture consisting of styrene (47.5 pts), ethylhexylacrylate (25 pts), 2-hydroxyethylmethacrylate (10 pts) and dimethylaminoethylmethacrylate (7.5 pts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (57.5 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further l hour and a further charge of azobis(isobutyronitrile) ~0.5 pts) and butoxyethanc)l added. This procedure is repeated twice more and the reaction mixture held a 100C for a further 1 hour at 100C and then cooled. The amine value of the resulting solution is 0.28 eq/kg and the molecular weight of the copolymer is 10.416.
Resin 7 A monomer mixture consisting of styrene (40 pts), ethylhexylacrylate (32.5 pts), 2-hydroxyethylmethacrylate (20 pts) and dimethylaminoethylmethacrylate (7.5 ts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (57.5 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for ~ further l hour and a further charge of azobis(isobutyronitrile) (0.5 pts) and butoxyethanol added. This procedure is repeated twice more and the reaction mixture held a lOO~C for a further 1 hour at 100C and then cooled. The amine value of the resulting solution is 0.28 eq/kg and the molecular weight of the copolymer is 10.307.
~9~S~7 Resin 8 A monomer mixt~re consisting of styrene (55 pts), ethylhexylacrylate (20 pts), 2-hydroxyethylmethacrylate (20 pts) and dimethylaminoethylmethacrylate (5 pts) with azobis(isobutyronitrile) (1.5 pts) is added drop~ise over 2 hours to butoxyethanol (50 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (0.5 pts) in butoxy ethanol (10 pts) added.
This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (20 pts) ~o reduce the solids content to around 50 V/o and stripped on a rotary evaporator under vacuum to remove any monomers still present. The amine value of the resulting solution is 0.15 e4/kg.
Resin 9 A monomer consisting of styrene (35 pts), butylacrylate (35 pts), 2-hydroxyethylmethacrylate (15 pts) and dimethylaminoethylmethacrylate (15 pts) wlth azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (50 pts) stirred uncler nitrogen at 100C. The reaction mixture is maintained at 100C for a further 1 hour snd a further chargc of azobis(isobutyronitrile) (0.5 pts) in butoxyethanol (10 pts) added. This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (20 pts) to reduce the solids content to around 50 % and stripped on a rotary evaporator under vacuum to remove any monomers still presant. The amine value of the resulting solution is 0.45 e4/kg.
Resin 10 -A monomer mixture consis~ing of methylmethacrylate (66 pts), butylacrylate (26.2 pts), and dimethylaminoethylmethacrylate (7.8 pts) with azobis~isobutyronitrile) (1.0 pts) i8 added dropwise over 3 and half hours to butoxy-ethanol (60 pts) at 105C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (0.1 pts) in butoxyethanol (4 pts) added. After a further 1 hour at 105C the ~8~
mixture is stripped on a rotary evaporator under vacuum to remove any monomers still present. The amine value of the resulting solution is 0.30 e~/kg.
Resin 11 . .
A monomer mixture consisting of styrene (15 pts), methylmethacrylate (27.5 pts), ethylhexyl acrylate (30 pts), 2-hydroxyethyl methacrylate (20 pts~ and dimethylaminoethylmethacrylate (7.5 pts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (50 pts) at 100C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (0.5 pts) in butoxyethanol (5.5. pts) added. After a further 1 hour at 100C the mixture is cooled. The amine value of the resulting solution is 0.28 eq/kg and the molecular weight of the copolymer is 10.348.
Example 1~ An aqueous developable negative working photoresist composition i9 prepared from:
triethylene glycol dimethacrylate20 pts benzophenone 4 pts Michler's Ketone 1 pts Styrene/butyl maleate copolymer 75 pts (available from Monsanto as Scripset 5~0) methyl ethyl ketolle 200 pts This is coated on a copper clad laminate using a wire-wound rod and dried at 90C for 5 minutes to produce a film 8 micrometers thick.
The film ls irradiated through an image bearing transparency for 30 seconds using a 5000 w medium pressure mercury halide lamp at a distance of 75 cm. On immersing in a 0.5 % aqueous solution of sodium hydroxide at 25C photoresist is removed from unirradiated areas so that copper is exposed in those areas and a clear negative image of the transparency is formed.
i7 ~ 1489-7166 The image bearing copper clad laminate is then immersed as the anode in an electrodeposition bath equipped with a stainless steel cathode and containing the following solution Resin 1 50 pts butoxyethanol 50 pts potassium hydroxide (20 % aqueous)7.9 pts water 392.1 pts voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 1.5 % aqueous solution of sodium hydroxide at 25C. This treatment removes the photoresist, leaving the electrodeposited resin.
The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion for 5 minutes in S % aqueous sodium hydroxide completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 2: A copper clad laminate coated with a RISTON negative aqueous developable photoresist which has been imaged and developed to form a pattern in the RISTON~ photoresist is used as the cathode in an electrodeposition bath equipped with a stainless steel anode.
The electrodeposition bath contains the following solution:
Resin 2 40 pts butoxyethanol 30 pts lactic acid (15 % aqueous) 13 pts water 317 pts A voltage of 40 volts is applied for 60 seconds, the copper clad laminate removed from the bath~ rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where the copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodepo~ited resin.
The exposed copper i8 etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pat-tsrn, in copper, on the laminate base.
Example 3: A copper clad laminate coated w'th a ~iston aqueous developable ne~ative photoresist which has been imaged and developed to form a pattern in the Riston photoresist is used as the cathode in an electrodeposition bath equipped with a stainless steel anode.
The electrodeposition bath contain~ the following solution:
Resin 3 100 pts lactic acid (20 % aqueous) 6.6 pts water 393.4 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in an etch bath at bOC containing ammonium psrsulphate (125 g), phosphoric acid (75 %
- 25 cm3) made up to 500 cm3 with water. After rinsing in water and drying, immsrsion in a bath of acetone completely removes rssidual resin, leaving a clear pattern, in copper, on the laminate base.
Following the procedure of Example 3 a RISTON~coated laminate is used tG obtain an image of the original photoresist in electrodeposited Resin 3. The exposed copper is etched away by immersion in a bath at 70C containing hydrogen peroxide (30 % -200 g), phosphoric acid (75 % - 200 g) and potassium permanganate (0.006 g) made up to 1 litre with water. After rinsing in water and drying, immersion in a bath of acetone completely removes residual resin, leaving a clear pat~ern, in copper, on the laminate base.
Example_5 Following the procedurs of ~xample 3 a RISTON-coated laminate is used to obtain an image in electrodeposited Resin 3 of the original photoresist. The exposed copper is etched away by immersion in a bath at 25C containing ammonium chloride (21.4 g), ammonia (25 % - 12 g), hydrogen peroxide (30 % - 12 cm3) and water (150 g). After rinsing in water and drying, immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 6: A copper clad laminate coated with a RISTON aqueous developable negative photoresist which has been imaged and developed to form a pattern ln the RISTON photoresist i9 used as the anode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 4 100 pts potassium hydroxide (20 % aqueous) 5.2 pts water 394.8 pts A voltage of 80 volts is applied for 60 seconds, the copper clad laminate removed from the bath rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the pho-toresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 7: A copper clad laminate coated with a RISTON negative photoreslst which has been imaged and developed to form a pattern in the RISTON photoresist is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 5 60 pts butoxyethanol 50 pts lactic acid (20 % aqueous) 15.8 pts water 474.2 pts A voltage of 30 volts is applied for 60 seconds, the copper laminate removed from the bath, rinsed with water and dried at 90C for 5 minutes. The electrodeposited resin fills the areas where copper i9 exposed. The laminate is then immersed in a stirred bath containirlg a solvent mixture consisting of 1,1,1-trichloroethane and dich10romethane (80:20). This treatment removes the photoresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate.
Example 8: A positive-working photoresist composition is prepared by mixing the reaction product of 1,2-naphthoquinone-2-diazide-5-sulphonyl chloride and 2,3,4-trihydroxybenzophenone - degree of esterification 2.5 mole with a p-tert.butyl phenol~ phenol novolak (mole ratio 0.25:0.75) such that the ratio of novolak to sensitizer is 5:1. The mixture is 5~
dissolved in a solvent blend of 2-ethoxyethanol, 2-ethoxyethanol acetate and methyl ethyl ketone (volume ratio 2:2:1) to obtain a solutlon of 40 % sollds by welght. The solutlon is applied by a wire wound rod to a copper clad laminate and the laminate dried at 90C
for 5 mlnutes, giving a resin Eilm 30 micrometers thick. It is then irradiated through a image-bearing transparency for 30 seconds, using a 5000 ~ medlum pressure mercury halide lamp at a distance of 75 cm. The laminate is lmmersed in a bath containing 0.5 % aqueous sodium hydroxide for 1 minute after whlch tlme a posltive image develops.
The image-bearing copper clad laminate is then immersed as the cathode in an electrodeposition bath equipped with a stalnless steel anode and containing the following solution:
Resln 3 100 pts lactic acid (20 % aqueous) 6.6 pts water 393.4 pts A voltage of S0 volts ls applled for 60 seconds, the copper clad lamlnate removed Erom the bath, rlnsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills th0 areas where copper ls exposed. The laminate is th0n imm0rsed in a stirred ~ath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate is washed ln water and dried. Immerslon in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
8~
Example 9: A copper clad laminate with a RISTON aqueous developable negatlve photoresist, which has been imaged and developed to form a pattern in the RISTON photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 3 100 pts lactic acid (20 %) 6.6 pts water 393.4 pts A voltage of 50 volts is applied for 50 seconds, the copper clad laminate removed from the bath and rinsed with water. The electrodeposited resin fills the areas where coppsr is exposed.
The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited resin. The laminate is dried at 90C for 5 minutes. The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30~C, a~ter which the plate is washed in water. Immersion in a bath of acetone completely remove~s residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 10: A copper clad laminate with a RI~TON aqueous developable negative photoresist, which has been imaged and developed to form a pattern in the RISTON photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 3 100 pts lactic acid (20 %) 6.6 pts water 393.4 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath and rinssd with water. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes thP
photoresist leaving the electrodeposited resin. The exposed copper i7 is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate ls washed in water.
Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
_ample 11- A copper clad laminate with a RISTON aqueous developable negative photoresist, which has been imaged and deYeloped to form a pattern in the RISTON photoresist, is used as the cathode is an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 6 100 pts lactic acicl (20 % aqueous) 16.8 pts water 483.2 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath, rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution o~ potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited film.
The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 12: Fxample 11 is repeated except that the voltage applied is 20 volts for 60 seconds. A clear pattern, in copper, is again obtained on the laminate base.
-Example 13: Example 11 is repeated except that the voltage applledis 120 volts for 60 seconds. A clear pattern, in copper, is again obtalned on tha laminate base~
~L298~ 7 Exame_e 14: Example 11 is repeated except that a double sided copper c]ad laminate with through holes with a RISTON aqueous developable negative photoresist, which has been imaged and developed, on both sides is used. A c]ear pattern, in copper, on both sides of the laminate base and in the through holes is obtained.
Example 15: A copper clad laminate with a RISTON aqueous developable negative photoresist, which has been imaged and developed to form a pattern in the RISTON photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 7 100 pts lactic acid (20 % aqueous) 16.8 pts water 483.2 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath, rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited film.
The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate i9 washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 16: Fxample 15 is repeated except that the electrodeposition bath contains the following solution:
Resin 8 100 pts lactic acid (20 % aqueous) 6.6 pts water 393.4 pts And a voltaga of 30 volts is applied for 60 seconds. A clear pattern, in copper, on the laminate base is obtained.
~8S67 Exarnple 17 Exan)ple 15 is repeated except that the electrodeposition bath contains the following solution:
Resln 9 100 pts lactic acid (20 % aqueous) 13.8 pts water 386.2 pts And a voltage o~ 40 volts is applied for 60 seconds. A clear pattern, in copper, on the laminate base is obtained.
18. Example 15 is repeated except that the electrodeposition bath contains the following solution:
Resin 10 100 pts lactic acid (20 % aqueous) 9 pts water 391 pts A clear pattern, in copper, on the laminate base is obtained.
Example 19: Example 15 is sepeated except that the electrodeposition bath contains the following solution:
Rssin 11 100 pts lactic acid (20 % aqueous) 6.7 pta water 493.3 pts A clear pattern, in copper, on the laminate base is obtained.
Example 20: A copper clad laminate with a RISTON aqueous developable negative photoresist, which has been imaged and devsloped to form a pattern in the RISTON photoreslst, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the ~ollowing aolution:
Resin 6 lQO pts lactic acid (20 % aqueous) 16.8 pts water 383.2 pts ~2~8S~7 A voltage of 2 volts is applied for 2 minutes and then a voltage of 5 volts is applied for 4 minutes. The laminate i5 removed from the bath, rinsed with water and dried at 90C for S minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited film. The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
There are numerous methods used for the manufacture of printed circ~it boards, although some of the steps used are common to the various methods.
In the case of single sided printed circuit boards, the board, comprising a copper clad base laminate, has holes drilled where desired, a resist i8 coated on the copper in a predetermined pattern, uslng screen printing or photolmaging techniques, to give a board having bare copper in some areas and copper coated by the resist in remaining areas, the bare copper is then plated with a tin-lead alloy, the resist is then removed, the copper thereby exposed is etched USi11g an etchant which does not remove the tin-lead alloy, which i9 finally removed using a tin lead alloy stripper.
In ~the case of double sided, plated through hole printed circuit boards, the procedure is slmilar, but with the following additional steps-after the holes are drilled the board is subjected to electroless copper deposition to deposit copper on the surface of the holes ( as well as over all the copper~and after applying the resist in a ~LZ985~i~
predetermined pattern the board is subjected to copper electroplat-ing to deposit copper on the bare copper parts including the surface of the holes.
Disadvantages of these processes are the high cost of the tin-lead alloy stripper and the necessary subsequent cleaning; and the tin-lead stripper (usually a mixture of hydrogen peroxide and sulphuric acid) is aggressive to the boards themselves and to personnel and equipment used in carrying out the stripping.
Ue have now found that the copper left bare after applying a photoresist can be protected by electrodeposition of an electrode-positable resin that is strippable by a different solvent from that used to strip the photoresist, and which is not removed by the copper etchant.
Electrodepositable resins have been known for many years and are commonly used for coating metal articles e.g. painting car bodies and accessories, steel girders, and household items such as washing machines. In all these uses the resin is electrodeposited and then cured. There has been a proposal in Russian Patent Specification No. 293312 to use an electrodepositable resin to protect exposed copper during the manufacture of a printed circuit board, but again, after electrodeposition the resin is thermally cured. This makes removal dificult and conditions are needed, an alkaline solution at 70 to 80C, which can damage the base laminate of a circuit board.
~e have found that sufficient protection can be given without substantially curing the electrodeposited resin.
Accordingly the present invention provides a method for making a metallic pattern on a substrate having a surface comprising bare metal in predetermined areas and metal coated by a photoresist in remaining areas which comprises (i) protecting the bare metal by electrodepositing a resin thereon, (ii) while leaving the electrodeposited resin substantially uncured, removing the resist ~.'' ~Z9~35;~
21~89-7166 from said remaining areas using a solvent which will not remove the electrodeposited resin, thereby exposing metal in said remaining areas, (iii) etching the metal exposed in (ii) using an etchant which does not remove the electrodeposited resin, and (iv) removing the electrodeposited resin with a suitable solvent.
The photoresist is coated in selected areas by applying it uni-formly to the substrate, which is usually a copper-clad laminate, subjecting it to actinic radiation, in a predetermined pattern and then removing exposed or unexposed areas according to whether the photoresist is positive or negative respectively. Positive and negative photoresists for use in making printed circuit boards are well known materials and any of them may be used. They can be strippable under aqueous conditions or by means of an organic solvent. A layer of another metal such as nickel may be deposited on bare copper areas before electrodeposition of the resin.
The electrodepositable resin may be anodically depositable or cathodically depositable, which are base-strippable and acid-strippable respectively. Anodically depositable resins are preferred if acidic etchants are to be used, and cathodic types are preferred if alkaline etchants for copper are to be used.
A particularly combination is the use of a photoresist which is strippable under aqueous conditions and an electrodepositable resin which is strippable by means of an organic solvent.
Any of the large number of electrodepositable resins may be used including acrylic resins; adducts of epoxide resins with amines or polycarboxylic, amino or mercapto acids; polyurethanes; polyester;
and reaction products of phenolic hydroxyl group-containin~ resins with an aldehyde and amine or amino- or mercapto-carboxylic acids.
Suitable acrylic resins include copolymers of at least one acrylic ester such as an alkyl or hydroxyalkyl acrylate or methacrylate with .~ , ~2~ 7 an ethylenically unsaturated monomer containing a salt-forming group, such as an acrylic monomer containing a carboxyl or tertiary amino group and, optionally, another ethylenically unsaturated monomer. Suitable epoxide resin adducts include those of diglycidyl ethers of dihydric alcohols or bisphenols with a stoichiometric excess of a primary or secondary monoamine or polyamine such as ethanolamine, diethanolamine or ethylenediamlne, a polycarboxylic acid such as glutaric or adipic acid, a polycarboxylic acid anhydride such as maleic or succinic anhydride, an aminocarboxylic acid such as o-, m- or p-aminobenzoic acid or a mercaptocarboxylic acid. Suitable polyurethanes include adducts of hydroxyl-terminated polyurethanes with polycarboxylic acid anhydrides. Suitable polyesters include carboxyl-terminated polyesters derived from polyhydric alcohols such as ethylene glycol, I,2-propylene glycol, 1,3-propylene glycol or butane-1,4-diol with polycarboxylic acids such as glutaric, adipic, maleic, tetrahydrophthalic and phthalic acids or esterlfying derivatives thereof. Suitable reaction products oE phenolic hydroxyl-containing resins include reaction products of phenol-terminated adducts of diglycidyl ethers with bisphenols, aldehydes such as formaldehyde or ben~aldehyde and amines such as ethanolamine, diethanolamlne or ethylene diamine, aminocarboxylic acids such as glycine, sarcosine or aspartic acid, or mercaptocarboxylic acids such as thioglycolic or 3-mercaptopropionic acid.
Preferred electrodepositable resins are copolymers of at least one monoacrylic ester, particularly selected from methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butyl acrylate, ethylhexyl acrylate and the corresponding methacrylates, with at least one monoacrylic monomer containing a carboxyl or tertiary amino group, particularly acrylic acid, methacrylic acid or dimethylaminoethyl methacrylate and, optionally, with a further vinyl monomer such as styrene. Other preferred electrodepositable resins are adducts of a diglycidyl ether of a bisphenol, particularly, bisphenol A, which may have been advanced, with 8 monoamine, particularly diethanolamine.
ilZ9~
The amount of resin deposited needs to be sufficient to cover the exposed metal completely and protect it during removal of the photoresist and during etching of the metal thereby exposed.
Electrodeposition for only a few minutes, usually one minute~ at a voltage of up to 200 volts is sufficient in most cases. Voltages as low as 2 volts may be used in some cases, especially if the size of the electrode on which the resin is deposited is small in relation to the other electrode. For example a cathodically depositable resin may be deposited on a small cathode in a tank where the whole of the tank is the anode, at voltages of 2 volts or 5 volts.
We have found that the adhesion of the coating is improved if it is deposited in two steps, first at a low voltage and then at a slightly higher voltage. For example a good coating can be obtained by electrodepositing the resin at 2 volts for 2 minutes, Eollowed by deposition at S volts for up to 5 minutes.
It is also possible to use a combination of a photoresist and an e].ectrodepositable resin which are both basic or both acidic strippable provided that the photoresist is strippable under milder conditions than are needed to remove the electrodeposited resin, e.g. a more dilute solution of base or acid.
The electrodeposited resin is pre~erably dried without curing it, for example by heating at a temperature up to 100C, before carrying out the etching step (iii), more preferably before removing the resist in step (ii).
When an organic solvent is used to remove the resist, a suitable solvent which does not dissolve the electrodeposited resin can be found by routing experimentation. Both this solvent and ~he solvent used to remove the electrodeposited resin can be selected from halohydrocarbons such as l,l,1-trichloroethane and dichloromethane, hydroxylic solvents such as 2-n-butoxyethanol and 2-ethoxyethanol, i7 esters such as 2-ethoxyethyl acetate, ketones such as acetone and methyl ethyl ketone and ethers such as tetrahydrofuran. Where, for example, the electrodeposited resin is derived from an epoxy resin and the resist is an acrylic material, the resist can be removed using a halohydrocarbon solvent and the electrodeposited resin can be removed USillg a ketone.
The metal exposed by removal of the resist, usually copper, may be removed by any well known etchant such as ferric chloride, hydrogen peroxidelphosphoric acid, ammonium persulphate or cupric chloride.
The present invention is also very useful for use with multilayer circuit boards, especially when via holes and through contacts are present.
The invention is illustrated by the following Examples in which parts are parts by weight. Th0 resins used in the Examples are:
Res1n 1 Methyl methacrylate (55 pts), methacrylic acid (5 pts), 2-hydroxyethyl methacrylate (40 pts) and tsrt.dodecylmercaptan (0.03 pts) are heated to reflux in tetrahydrofuran (THF) ~350 pts).
Azobis(isobutyronitrile) (I.5 pts~ i9 added and the mixture maintained at reflux for 5 hours under nitrogen. The reaction mixture is cooled to ambient temperature and added slowly to stirred hexane (900 pts). A precipitate i9 formed which is filtered off and washed with further hexane. The product is dried at 40C in a vacuum oven to yield 87 pts of a copolymer-acid value 0.56 eqlkg, molecular weight (number average) 7206.
Resin 2 -Styrene (50 pts), dimethylaminoethyl methacrylate (10 pts), ethylhexyl methacrylate (20 pts), 2-hydroxypropyl methacrylate ~20 pts) and tert.dodecylmercaptan (0.03 pts) are dissolved in THF
(340 pts). Azobis(isobutyronitrile) (1.5 pts) in THF (10 pts) is added and the mixture held at re~lux for 5 hours under nitrogen. The :~9~
reaction mixture is stripped under vacuum to obtain a resinous solid which i5 further dried in a vacuum oven at 40C. The solid copolymer obtained has an amine value 0.22 eq/kg and molecular weight (number average) 14,538.
Resin 3 A monomer mixture consisting of styrene (26.25 pts), ethylhexyl acrylate (10 pts), 2-hydroxyethyl methacrylate (10 pts) and dimethylaminoethyl methacrylate (3.75 pts) with azobis(isobutyronitrile) (0.75 pts) is added dropwise over 2 hours to butoxyethanol (25 pts~ stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further hour and further charge of azobis(isobutyronitrile) (0.25 pts) and butoxyethanol (5.0 pts~ added. This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (10 pts) to reduce solids to around 50 % and stripped on a rotary evaporator under vacuum to remove any monomers still present. The amine value of the resulting solution is 0.23 eq/kg and the molecular weight (number average) of the copolymer is 9410.
Resin 4 A monomer mixture consisting of methyl methacrylate (46 pts), butyl acrylate (50 pts), methacrylic acid (~ pts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (25 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (1.5 pts) in butoxyethanol (10 pts) added. This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (20 pts) to reduce solids content to around 50 % and stripped on a rotary ~vaporator under vacuum to removed any monomers still present. The acid value of the resulting solution is 0.23 eq/~g and the molecular weight of the copolymer is 13,276.
~8567 Resin 5 An epoxide resin prepared by advancing a diglycidyl ether of bisphenol A by reaction with bisphenol A (epoxy value 0.99 mol/kg, 100 g) is heated to 140C together with butoxyethanol (60 g) to form a solution. To this is added a solution of diethanolamine (10.7 g) in butoxyethanol (13.8 g) and the temperature of the mixture maintained at 140C for a further 4 hours, after which tims it is cooled. The resulting solution has an amine value of O.S5 mol/kg and an epoxy value of zero.
Resin 6 A monomer mixture consisting of styrene (47.5 pts), ethylhexylacrylate (25 pts), 2-hydroxyethylmethacrylate (10 pts) and dimethylaminoethylmethacrylate (7.5 pts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (57.5 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further l hour and a further charge of azobis(isobutyronitrile) ~0.5 pts) and butoxyethanc)l added. This procedure is repeated twice more and the reaction mixture held a 100C for a further 1 hour at 100C and then cooled. The amine value of the resulting solution is 0.28 eq/kg and the molecular weight of the copolymer is 10.416.
Resin 7 A monomer mixture consisting of styrene (40 pts), ethylhexylacrylate (32.5 pts), 2-hydroxyethylmethacrylate (20 pts) and dimethylaminoethylmethacrylate (7.5 ts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (57.5 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for ~ further l hour and a further charge of azobis(isobutyronitrile) (0.5 pts) and butoxyethanol added. This procedure is repeated twice more and the reaction mixture held a lOO~C for a further 1 hour at 100C and then cooled. The amine value of the resulting solution is 0.28 eq/kg and the molecular weight of the copolymer is 10.307.
~9~S~7 Resin 8 A monomer mixt~re consisting of styrene (55 pts), ethylhexylacrylate (20 pts), 2-hydroxyethylmethacrylate (20 pts) and dimethylaminoethylmethacrylate (5 pts) with azobis(isobutyronitrile) (1.5 pts) is added drop~ise over 2 hours to butoxyethanol (50 pts) stirred under nitrogen at 100C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (0.5 pts) in butoxy ethanol (10 pts) added.
This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (20 pts) ~o reduce the solids content to around 50 V/o and stripped on a rotary evaporator under vacuum to remove any monomers still present. The amine value of the resulting solution is 0.15 e4/kg.
Resin 9 A monomer consisting of styrene (35 pts), butylacrylate (35 pts), 2-hydroxyethylmethacrylate (15 pts) and dimethylaminoethylmethacrylate (15 pts) wlth azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (50 pts) stirred uncler nitrogen at 100C. The reaction mixture is maintained at 100C for a further 1 hour snd a further chargc of azobis(isobutyronitrile) (0.5 pts) in butoxyethanol (10 pts) added. This procedure is repeated twice more. The reaction mixture is diluted with butoxyethanol (20 pts) to reduce the solids content to around 50 % and stripped on a rotary evaporator under vacuum to remove any monomers still presant. The amine value of the resulting solution is 0.45 e4/kg.
Resin 10 -A monomer mixture consis~ing of methylmethacrylate (66 pts), butylacrylate (26.2 pts), and dimethylaminoethylmethacrylate (7.8 pts) with azobis~isobutyronitrile) (1.0 pts) i8 added dropwise over 3 and half hours to butoxy-ethanol (60 pts) at 105C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (0.1 pts) in butoxyethanol (4 pts) added. After a further 1 hour at 105C the ~8~
mixture is stripped on a rotary evaporator under vacuum to remove any monomers still present. The amine value of the resulting solution is 0.30 e~/kg.
Resin 11 . .
A monomer mixture consisting of styrene (15 pts), methylmethacrylate (27.5 pts), ethylhexyl acrylate (30 pts), 2-hydroxyethyl methacrylate (20 pts~ and dimethylaminoethylmethacrylate (7.5 pts) with azobis(isobutyronitrile) (1.5 pts) is added dropwise over 2 hours to butoxyethanol (50 pts) at 100C. The reaction mixture is maintained at 100C for a further 1 hour and a further charge of azobis(isobutyronitrile) (0.5 pts) in butoxyethanol (5.5. pts) added. After a further 1 hour at 100C the mixture is cooled. The amine value of the resulting solution is 0.28 eq/kg and the molecular weight of the copolymer is 10.348.
Example 1~ An aqueous developable negative working photoresist composition i9 prepared from:
triethylene glycol dimethacrylate20 pts benzophenone 4 pts Michler's Ketone 1 pts Styrene/butyl maleate copolymer 75 pts (available from Monsanto as Scripset 5~0) methyl ethyl ketolle 200 pts This is coated on a copper clad laminate using a wire-wound rod and dried at 90C for 5 minutes to produce a film 8 micrometers thick.
The film ls irradiated through an image bearing transparency for 30 seconds using a 5000 w medium pressure mercury halide lamp at a distance of 75 cm. On immersing in a 0.5 % aqueous solution of sodium hydroxide at 25C photoresist is removed from unirradiated areas so that copper is exposed in those areas and a clear negative image of the transparency is formed.
i7 ~ 1489-7166 The image bearing copper clad laminate is then immersed as the anode in an electrodeposition bath equipped with a stainless steel cathode and containing the following solution Resin 1 50 pts butoxyethanol 50 pts potassium hydroxide (20 % aqueous)7.9 pts water 392.1 pts voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 1.5 % aqueous solution of sodium hydroxide at 25C. This treatment removes the photoresist, leaving the electrodeposited resin.
The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion for 5 minutes in S % aqueous sodium hydroxide completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 2: A copper clad laminate coated with a RISTON negative aqueous developable photoresist which has been imaged and developed to form a pattern in the RISTON~ photoresist is used as the cathode in an electrodeposition bath equipped with a stainless steel anode.
The electrodeposition bath contains the following solution:
Resin 2 40 pts butoxyethanol 30 pts lactic acid (15 % aqueous) 13 pts water 317 pts A voltage of 40 volts is applied for 60 seconds, the copper clad laminate removed from the bath~ rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where the copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodepo~ited resin.
The exposed copper i8 etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pat-tsrn, in copper, on the laminate base.
Example 3: A copper clad laminate coated w'th a ~iston aqueous developable ne~ative photoresist which has been imaged and developed to form a pattern in the Riston photoresist is used as the cathode in an electrodeposition bath equipped with a stainless steel anode.
The electrodeposition bath contain~ the following solution:
Resin 3 100 pts lactic acid (20 % aqueous) 6.6 pts water 393.4 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in an etch bath at bOC containing ammonium psrsulphate (125 g), phosphoric acid (75 %
- 25 cm3) made up to 500 cm3 with water. After rinsing in water and drying, immsrsion in a bath of acetone completely removes rssidual resin, leaving a clear pattern, in copper, on the laminate base.
Following the procedure of Example 3 a RISTON~coated laminate is used tG obtain an image of the original photoresist in electrodeposited Resin 3. The exposed copper is etched away by immersion in a bath at 70C containing hydrogen peroxide (30 % -200 g), phosphoric acid (75 % - 200 g) and potassium permanganate (0.006 g) made up to 1 litre with water. After rinsing in water and drying, immersion in a bath of acetone completely removes residual resin, leaving a clear pat~ern, in copper, on the laminate base.
Example_5 Following the procedurs of ~xample 3 a RISTON-coated laminate is used to obtain an image in electrodeposited Resin 3 of the original photoresist. The exposed copper is etched away by immersion in a bath at 25C containing ammonium chloride (21.4 g), ammonia (25 % - 12 g), hydrogen peroxide (30 % - 12 cm3) and water (150 g). After rinsing in water and drying, immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 6: A copper clad laminate coated with a RISTON aqueous developable negative photoresist which has been imaged and developed to form a pattern ln the RISTON photoresist i9 used as the anode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 4 100 pts potassium hydroxide (20 % aqueous) 5.2 pts water 394.8 pts A voltage of 80 volts is applied for 60 seconds, the copper clad laminate removed from the bath rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the pho-toresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 7: A copper clad laminate coated with a RISTON negative photoreslst which has been imaged and developed to form a pattern in the RISTON photoresist is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 5 60 pts butoxyethanol 50 pts lactic acid (20 % aqueous) 15.8 pts water 474.2 pts A voltage of 30 volts is applied for 60 seconds, the copper laminate removed from the bath, rinsed with water and dried at 90C for 5 minutes. The electrodeposited resin fills the areas where copper i9 exposed. The laminate is then immersed in a stirred bath containirlg a solvent mixture consisting of 1,1,1-trichloroethane and dich10romethane (80:20). This treatment removes the photoresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate.
Example 8: A positive-working photoresist composition is prepared by mixing the reaction product of 1,2-naphthoquinone-2-diazide-5-sulphonyl chloride and 2,3,4-trihydroxybenzophenone - degree of esterification 2.5 mole with a p-tert.butyl phenol~ phenol novolak (mole ratio 0.25:0.75) such that the ratio of novolak to sensitizer is 5:1. The mixture is 5~
dissolved in a solvent blend of 2-ethoxyethanol, 2-ethoxyethanol acetate and methyl ethyl ketone (volume ratio 2:2:1) to obtain a solutlon of 40 % sollds by welght. The solutlon is applied by a wire wound rod to a copper clad laminate and the laminate dried at 90C
for 5 mlnutes, giving a resin Eilm 30 micrometers thick. It is then irradiated through a image-bearing transparency for 30 seconds, using a 5000 ~ medlum pressure mercury halide lamp at a distance of 75 cm. The laminate is lmmersed in a bath containing 0.5 % aqueous sodium hydroxide for 1 minute after whlch tlme a posltive image develops.
The image-bearing copper clad laminate is then immersed as the cathode in an electrodeposition bath equipped with a stalnless steel anode and containing the following solution:
Resln 3 100 pts lactic acid (20 % aqueous) 6.6 pts water 393.4 pts A voltage of S0 volts ls applled for 60 seconds, the copper clad lamlnate removed Erom the bath, rlnsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills th0 areas where copper ls exposed. The laminate is th0n imm0rsed in a stirred ~ath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited resin.
The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate is washed ln water and dried. Immerslon in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
8~
Example 9: A copper clad laminate with a RISTON aqueous developable negatlve photoresist, which has been imaged and developed to form a pattern in the RISTON photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 3 100 pts lactic acid (20 %) 6.6 pts water 393.4 pts A voltage of 50 volts is applied for 50 seconds, the copper clad laminate removed from the bath and rinsed with water. The electrodeposited resin fills the areas where coppsr is exposed.
The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited resin. The laminate is dried at 90C for 5 minutes. The exposed copper is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30~C, a~ter which the plate is washed in water. Immersion in a bath of acetone completely remove~s residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 10: A copper clad laminate with a RI~TON aqueous developable negative photoresist, which has been imaged and developed to form a pattern in the RISTON photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 3 100 pts lactic acid (20 %) 6.6 pts water 393.4 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath and rinssd with water. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes thP
photoresist leaving the electrodeposited resin. The exposed copper i7 is etched away by immersion in a 40 % aqueous solution of ferric chloride at 30C, after which the plate ls washed in water.
Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
_ample 11- A copper clad laminate with a RISTON aqueous developable negative photoresist, which has been imaged and deYeloped to form a pattern in the RISTON photoresist, is used as the cathode is an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 6 100 pts lactic acicl (20 % aqueous) 16.8 pts water 483.2 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath, rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution o~ potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited film.
The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 12: Fxample 11 is repeated except that the voltage applied is 20 volts for 60 seconds. A clear pattern, in copper, is again obtained on the laminate base.
-Example 13: Example 11 is repeated except that the voltage applledis 120 volts for 60 seconds. A clear pattern, in copper, is again obtalned on tha laminate base~
~L298~ 7 Exame_e 14: Example 11 is repeated except that a double sided copper c]ad laminate with through holes with a RISTON aqueous developable negative photoresist, which has been imaged and developed, on both sides is used. A c]ear pattern, in copper, on both sides of the laminate base and in the through holes is obtained.
Example 15: A copper clad laminate with a RISTON aqueous developable negative photoresist, which has been imaged and developed to form a pattern in the RISTON photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the following solution:
Resin 7 100 pts lactic acid (20 % aqueous) 16.8 pts water 483.2 pts A voltage of 50 volts is applied for 60 seconds, the copper clad laminate removed from the bath, rinsed with water and dried at 90C
for 5 minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited film.
The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate i9 washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Example 16: Fxample 15 is repeated except that the electrodeposition bath contains the following solution:
Resin 8 100 pts lactic acid (20 % aqueous) 6.6 pts water 393.4 pts And a voltaga of 30 volts is applied for 60 seconds. A clear pattern, in copper, on the laminate base is obtained.
~8S67 Exarnple 17 Exan)ple 15 is repeated except that the electrodeposition bath contains the following solution:
Resln 9 100 pts lactic acid (20 % aqueous) 13.8 pts water 386.2 pts And a voltage o~ 40 volts is applied for 60 seconds. A clear pattern, in copper, on the laminate base is obtained.
18. Example 15 is repeated except that the electrodeposition bath contains the following solution:
Resin 10 100 pts lactic acid (20 % aqueous) 9 pts water 391 pts A clear pattern, in copper, on the laminate base is obtained.
Example 19: Example 15 is sepeated except that the electrodeposition bath contains the following solution:
Rssin 11 100 pts lactic acid (20 % aqueous) 6.7 pta water 493.3 pts A clear pattern, in copper, on the laminate base is obtained.
Example 20: A copper clad laminate with a RISTON aqueous developable negative photoresist, which has been imaged and devsloped to form a pattern in the RISTON photoreslst, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode. The electrodeposition bath contains the ~ollowing aolution:
Resin 6 lQO pts lactic acid (20 % aqueous) 16.8 pts water 383.2 pts ~2~8S~7 A voltage of 2 volts is applied for 2 minutes and then a voltage of 5 volts is applied for 4 minutes. The laminate i5 removed from the bath, rinsed with water and dried at 90C for S minutes. The electrodeposited resin fills the areas where copper is exposed. The laminate is then immersed in a stirred bath of 3 % aqueous solution of potassium hydroxide at 40C. This treatment removes the photoresist leaving the electrodeposited film. The exposed copper is etched away by immersion in an etch bath containing 40 % aqueous ferric chloride at 30C, after which the plate is washed in water and dried. Immersion in a bath of acetone completely removes residual resin, leaving a clear pattern, in copper, on the laminate base.
Claims (12)
1. A method for making a metallic pattern on a substrate having a surface comprising bare metal in predetermined areas and metal coated by a photoresist in remaining areas which comprises (i) protecting the bare metal by electrodepositing a resin thereon, (ii) while leaving the electrodeposited resin substantially uncured, removing the photoresist from said remaining areas using a solvent which will not remove the electrodeposited resin, thereby exposing metal in said remaining areas, (iii) etching the metal exposed in (ii) using an etchant which does not remove the electrodeposited resin, and (iv) removing the electrodeposited resin with a suitable solvent.
2. A method as claimed in claim 1 in which the photoresist is a photoresist which is strippable under aqueous conditions or by means of an organic solvent.
3. A method as claimed in claim 1 in which the photoresist is strippable under aqueous conditions and the electrodeposited resin is strippable by means of an organic solvent.
4. A method as claimed in claim 1 in which the electrodepositable resin is an acrylic resin; an adduct of an epoxide resin with an amine, a polycarboxylic acid or anhydride, an aminocarboxylic acid or a mercaptocarboxylic acid; a polyurethane; a polyester; or a reaction product of a phenolic hydroxyl group-containing resin with an aldehyde and an amine or an amino- or mercapto-carboxylic acid.
5. A method as claimed in claim 4, in which the electrodeposited resin is a copolymer of at least one monoacrylic ester with at least one monoacrylic monomer containing a carboxyl or tertiary amino group and, optionally, with a further vinyl monomer.
6. A method as claimed in claim 4, in which the electrodeposited resin is an adduct of a diglycidyl ether of a bisphenol, which may have been advanced, with a monoamine.
7. A method as claimed in claim 1 in which the electrodeposition is carried out at a voltage of from 2 to 200 volts.
8. A method as claimed in claim 7 in which the electrodeposition is carried out in two stages, first at a low voltage and then at a slightly higher voltage.
9. A method as claimed in claim 1 in which the electrodeposited resin is dried without curing it before carrying out the etching step (iii).
10. A method as claimed in claim 9, in which the electrodeposited resin is dried before removing the resist in step (ii).
11. A method according to claim 1 in which the metallic pattern is a printed circuit and the metal is copper.
12. A method according to claim 11 in which the printed circuit is on a board having through holes.
F0 7.3/STA/cc*
F0 7.3/STA/cc*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8614868 | 1986-06-18 | ||
| GB868614868A GB8614868D0 (en) | 1986-06-18 | 1986-06-18 | Metallic patterns |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1298567C true CA1298567C (en) | 1992-04-07 |
Family
ID=10599672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000539829A Expired - Lifetime CA1298567C (en) | 1986-06-18 | 1987-06-16 | Method for making metallic patterns |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4746399A (en) |
| EP (1) | EP0250366A3 (en) |
| JP (1) | JPS632398A (en) |
| BR (1) | BR8703044A (en) |
| CA (1) | CA1298567C (en) |
| GB (1) | GB8614868D0 (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6323389A (en) * | 1986-07-16 | 1988-01-30 | 関西ペイント株式会社 | Method of forming printed circuit |
| JPH0770812B2 (en) * | 1986-08-08 | 1995-07-31 | 関西ペイント株式会社 | Method of forming printed circuit board |
| US4911785A (en) * | 1987-02-04 | 1990-03-27 | Andus Corporation | The method of forming a thin film artwork compounds |
| GB8801736D0 (en) * | 1988-01-27 | 1988-02-24 | Ciba Geigy Ag | Method of making patterns |
| JPH0234984A (en) * | 1988-04-13 | 1990-02-05 | Mitsubishi Electric Corp | Manufacture of printed circuit board |
| US4994349A (en) * | 1988-06-27 | 1991-02-19 | At&T Bell Laboratories | Printed wiring board fabrication method |
| GB8822145D0 (en) * | 1988-09-21 | 1988-10-26 | Ciba Geigy Ag | Method |
| GB8827847D0 (en) * | 1988-11-29 | 1988-12-29 | Ciba Geigy Ag | Method |
| GB8913090D0 (en) * | 1989-06-07 | 1989-07-26 | Ciba Geigy Ag | Method |
| EP0410274B1 (en) * | 1989-07-25 | 1995-11-15 | Dai Nippon Insatsu Kabushiki Kaisha | Method of forming fine patterns |
| GB8924142D0 (en) * | 1989-10-26 | 1989-12-13 | Ciba Geigy | Methods for making metallic patterns |
| US5055164A (en) * | 1990-03-26 | 1991-10-08 | Shipley Company Inc. | Electrodepositable photoresists for manufacture of hybrid circuit boards |
| JPH0476985A (en) * | 1990-07-18 | 1992-03-11 | Cmk Corp | Manufacture of printed circuit board |
| BR9103260A (en) * | 1990-08-02 | 1992-02-18 | Ppg Industries Inc | COMPOSITION OF PHOTOSENSITIVE RESIN THAT CAN BE ELECTRODEPOSITED AND CAN RECEIVE PHOTO IMAGE |
| US5268256A (en) * | 1990-08-02 | 1993-12-07 | Ppg Industries, Inc. | Photoimageable electrodepositable photoresist composition for producing non-tacky films |
| JPH04355990A (en) * | 1990-09-18 | 1992-12-09 | Fujitsu Ltd | Circuit board and manufacture thereof |
| JPH04146687A (en) * | 1990-10-08 | 1992-05-20 | Nippon Paint Co Ltd | Manufacture of solder masked circuit board |
| US5105537A (en) * | 1990-10-12 | 1992-04-21 | International Business Machines Corporation | Method for making a detachable electrical contact |
| US5288377A (en) * | 1991-06-05 | 1994-02-22 | Macdermid, Incorporated | Process for the manufacture of printed circuits using electrophoretically deposited organic resists |
| US5160579A (en) * | 1991-06-05 | 1992-11-03 | Macdermid, Incorporated | Process for manufacturing printed circuit employing selective provision of solderable coating |
| GB9114098D0 (en) * | 1991-06-29 | 1991-08-14 | Ciba Geigy Ag | Method of making patterns |
| HUT71621A (en) * | 1993-01-11 | 1996-01-29 | Ppg Industries Inc | Phosphating compositions and processes, particularly for use in fabrication of printed circuits utilizing organic resists |
| JP3583455B2 (en) * | 1994-02-01 | 2004-11-04 | 関西ペイント株式会社 | Circuit board manufacturing method |
| KR100238908B1 (en) * | 1994-03-16 | 2000-01-15 | 니시무로 타이죠 | Apparatus and method for assembling battery |
| US20080210565A1 (en) * | 2005-08-08 | 2008-09-04 | Shou-Hui Chen | Method of Surface Treatment for Metal and Nonmetal Surfaces |
| TWI342172B (en) * | 2007-01-02 | 2011-05-11 | Advanced Semiconductor Eng | Circuit board and method for manufacturing the same |
| JP6069070B2 (en) * | 2013-03-28 | 2017-01-25 | 日東電工株式会社 | Soft magnetic thermosetting adhesive film, magnetic film laminated circuit board, and position detection device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1194826A (en) * | 1966-08-09 | 1970-06-10 | Ronson Products Ltd | Improvements relating to Electro-Plating and Etching Processes |
| DE1665151B1 (en) * | 1967-08-08 | 1970-12-17 | Montan Forschung Dr Hans Zille | Process for the production of electrical components of the printed circuit type |
| US4751172A (en) * | 1986-08-01 | 1988-06-14 | Shipley Company Inc. | Process for forming metal images |
-
1986
- 1986-06-18 GB GB868614868A patent/GB8614868D0/en active Pending
-
1987
- 1987-06-08 US US07/059,646 patent/US4746399A/en not_active Expired - Fee Related
- 1987-06-12 EP EP87810337A patent/EP0250366A3/en not_active Ceased
- 1987-06-16 CA CA000539829A patent/CA1298567C/en not_active Expired - Lifetime
- 1987-06-17 BR BR8703044A patent/BR8703044A/en unknown
- 1987-06-18 JP JP62152392A patent/JPS632398A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB8614868D0 (en) | 1986-07-23 |
| EP0250366A2 (en) | 1987-12-23 |
| JPS632398A (en) | 1988-01-07 |
| EP0250366A3 (en) | 1990-02-07 |
| US4746399A (en) | 1988-05-24 |
| BR8703044A (en) | 1988-03-08 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |