WO1991014972A1 - Wässrig entwickelbares, negativ wirkendes, elektrophoretisch abscheidbares und photohärtbares beschichtungsmittel sowie seine verwendung zur herstellung von leiterbahnen - Google Patents

Wässrig entwickelbares, negativ wirkendes, elektrophoretisch abscheidbares und photohärtbares beschichtungsmittel sowie seine verwendung zur herstellung von leiterbahnen Download PDF

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Publication number
WO1991014972A1
WO1991014972A1 PCT/EP1991/000505 EP9100505W WO9114972A1 WO 1991014972 A1 WO1991014972 A1 WO 1991014972A1 EP 9100505 W EP9100505 W EP 9100505W WO 9114972 A1 WO9114972 A1 WO 9114972A1
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Prior art keywords
weight
component
ethylenically unsaturated
coating agent
polymer
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PCT/EP1991/000505
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German (de)
English (en)
French (fr)
Inventor
Horst HINTZE-BRÜNING
Stephan Schunck
Bernd-Rüdiger VOLKMANN
Monika HOPPE-HÖFFLER
Original Assignee
Basf Lacke + Farben Aktiengesellschaft
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Application filed by Basf Lacke + Farben Aktiengesellschaft filed Critical Basf Lacke + Farben Aktiengesellschaft
Priority to KR1019920702314A priority Critical patent/KR960014055B1/ko
Priority to BR919106275A priority patent/BR9106275A/pt
Priority to JP3506290A priority patent/JPH087440B2/ja
Publication of WO1991014972A1 publication Critical patent/WO1991014972A1/de

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/164—Coating processes; Apparatus therefor using electric, electrostatic or magnetic means; powder coating
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to an aqueous developable, negative-acting, electrophoretically depositable and photocurable coating agent which
  • the present invention also relates to the use of these coating compositions for the production of conductor tracks.
  • Printed circuit boards have become very important in the manufacture of electronic devices.
  • the conventional printed circuit boards are based on glass fiber epoxy laminates or other laminates.
  • the function of these printed circuit boards is primarily that of a flat, two-dimensional carrier and connecting element for the individual electronic components, such as, for example, capacitors, transistors and resistors.
  • capacitors transistors and resistors
  • other electrical and structural elements are required.
  • Such two-dimensional circuit boards are produced, for example, by electrophoretically depositing a photo-curable lacquer film on a copper-clad layer and exposing it through a mask.
  • the printed circuit pattern is then developed by removing the unexposed areas in the case of the negative-acting photoresist materials or the exposed areas in the case of the positive-acting photoresist materials.
  • the exposed copper surfaces are then removed by treatment with an acidic etching solution.
  • the printed circuit is then obtained by removing the remaining layer of lacquer.
  • Such a method for producing the 2-dimensional printed circuit boards using negatively acting, water-developable, electrophoretically separable and photocurable resist materials is described, for example, in EP-B-176 356.
  • An aqueous solution or emulsion is used as the resist material from a preferably saturated polymer with carrier groups, an acid or base for neutralizing the carrier groups, a photoinitiator and an unsaturated crosslinking monomer.
  • Linear acrylate polymers, vinyl polymers, epoxy resins, polyurethanes and polyesters are mentioned as examples of suitable polymers.
  • these photoresist materials described in DE-OS 3715412 contain a water-soluble or water-dispersible, polymerizable unsaturated resin with an acid number of 20 to 300, an unsaturation equivalent of 150 to 300 and a number-average molecular weight of not less than 300, possibly one unsaturated monomeric compound and a water-insoluble photopolymerization initiator.
  • the photoresist materials described in DE-OS 3715412 have the disadvantage that the deposition voltages which can be achieved to achieve sufficiently high dry film layer thicknesses ( " , 30. Um) have very low values due to the low tear-off voltages of these materials As a result, these materials show poor wrap.
  • the 2 1 / 2- and 3-dimensional printed circuit boards represent a further development of the conventional printed circuit boards.
  • Such printed circuit boards are injection molded parts made of thermoplastic materials that are selectively metallized. Functionally they unite: PCB, connector, "chip carrier” as well as mechanical and structural elements. Since the shape of the part, the cutouts, the holes etc. are located in the precision injection molding tool, the accuracy and reproducibility from one part to the other is excellent.
  • a high deposition voltage (depending on the molded part between 250 in general) and 300 V) of the photoresist materials are necessary since this is the only way to achieve a good wrap.
  • the photoresist materials used must have a breakdown voltage of at least 300 to 350 V, depending on the molded part.
  • US Pat. No. 4,040,925 discloses anodically depositable, photocurable coating compositions based on unsaturated linear or branched acrylate polymers with an average molecular weight of 170 to 100,000.
  • the coating compositions described there lead to coatings with high hardness and good solvent resistance.
  • the use or suitability of these coating compositions as a photoresist material is not described in US Pat. No. 4,040,925.
  • US Pat. No. 4,039,414 discloses photo-curable coating compositions which can be deposited cathodically and are based on unsaturated linear or branched acrylate polymers with an average molecular weight of 170 to 100,000. The use or suitability of these coating compositions as photoresist material is also not described.
  • the present invention is therefore based on the object of providing aqueous, developable, negative-acting, electrophoretically separable and photocurable photoresist materials which have a maximum tear-off voltage of at least 300 to 350 V, depending on the molded part, and have good wrap-around behavior. Furthermore, these photoresist materials must cure as quickly as possible and show good and rapid strippability and developability with good resistance to the commonly used etching and electroplating baths. This object is surprisingly achieved by an aqueous developable, negative-acting, electrophoretically depositable and photocurable coating agent which
  • polymer A has a double bond equivalent of 1,500 to 10,000 and a content of anion- or cation-forming groups of Has 0.5 to 5.0 milliequivalents / g and can be produced by
  • the present invention also relates to a method for producing a printed circuit, in which these coating compositions according to the invention are deposited electrophoretically on the copper surface and by irradiating and developing a poly
  • the present invention relates to the use of these coating compositions as a photoresist material and for the production of 2-, 2 1 / 2- and 3-dimensional conductor tracks.
  • these coating compositions show high tear-off voltages of at least 300 to 350 V, depending on the molded part to be coated, and good wrap-around behavior and at the same time cure very quickly, and good and fast stripping and Show developability.
  • these coating compositions according to the invention in particular 2 1/2 and 3-dimensional, but also 2-dimensional conductor tracks can be produced using a simple and economical process. Due to the high tear-off voltage of the coating compositions, relatively high deposition voltages can be used, which are important for achieving uniform layer thicknesses even on the surfaces facing away from the electrode and in cavities. However, these required deposition voltages are sufficiently distant from the break-off voltage, so that problems in the case of anodic deposition are largely avoided by oxidation of the copper ions.
  • the polymerizable unsaturated resin A used according to the invention can be prepared by first by free radical solution polymerization at temperatures of generally 70 to 200 ° C., preferably 100 to 150 ° C., of the monomers a to a. a copolymer is produced.
  • Suitable monomers a with at least two ethylenically unsaturated polymerizable double bonds per molecule and a number average molecular weight of less than 400 are compounds of the general formula
  • R H or CH 3
  • R 1 , R 2 H, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH- (CH 3 ) 2
  • Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, glycol diacrylate, glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.
  • Divinyl compounds such as e.g. Divinylbenzene, suitable as component a. Mixtures of multifunctional monomers can of course also be used.
  • Component a can also be a reaction product of a carboxylic acid with a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and / or glycidyl methacrylate.
  • Component a can furthermore be a polycarboxylic acid esterified with an unsaturated alcohol containing a polymerizable double bond or an unsaturated monocarboxylic acid esterified with an unsaturated alcohol containing a polymerizable double bond.
  • component a the reaction product of two moles of acrylic or methacrylic acid with one mole of bisphenol A or bisphenol F diglycidyl ether is also suitable.
  • Alkoxylated bisphenol A or bisphenol F di (meth) acrylate can also be used as component a.
  • Reaction products of a polyisocyanate with unsaturated, polymerizable double bonds containing alcohols or amines can also be used as component a.
  • An example of this is the reaction product of one mole of hexamethylene diisocyanate and two moles of allyl alcohol.
  • Preferred components A are compounds having 5 min- desten ⁇ two methacryloyl groups per molecule.
  • Component a is used in amounts of 5 to 30% by weight, preferably 10 to 20% by weight, based on the total weight of the sum of components a to a 4 .
  • Monomers which have an anion- or cation-forming group are preferably used as component a_.
  • suitable monomers a 2 which contain an anion-forming group are monomers containing carboxyl groups, such as, for example, acrylic, methacrylic, maleic, fumaric, crotonic, isoerotonic and dimethylacrylic acid, and also succinic acid mono (meth) acryloyloxyethyl ester , Phthalic mono (meth) acryloyloxyethyl ester and reaction products of phthalic anhydride or succinic anhydride with hydroxyalkyl (meth) acrylic lat / £ caprolactone adducts, such as, for example, the product commercially available under the brand name TONE M100 from Union Carbide.
  • carboxyl groups such as, for example, acrylic, methacrylic, maleic, fumaric, crotonic, isoerotonic and dimethylacrylic acid
  • succinic acid mono (meth) acryloyloxyethyl ester Phthalic mono (meth) acryloyloxye
  • Derivatives of phosphoric and sulfuric acid are also suitable, such as, for example, hydroxyalkyl (meth) acrylate phosphoric acid monoester and hydroxyalkyl (meth) acrylate sulfuric acid monoester.
  • Acrylic and methacrylic acid are preferably used.
  • Monomers which can form cations are also suitable as component a 2 .
  • Mono-containing monomers are preferably used as cation-forming monomers.
  • suitable monomers a 2 containing amino groups are N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylamino-propyl (meth) acrylate, N-2-tert-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl ( meth) acrylamide and p-dimethylaminostyrene.
  • monomers can also be used as component a 2 which do not contain an anion- or cation-forming group, but contain another functional group, such as a hydroxyl, epoxy or isocyanate group.
  • Suitable monomers a 2 containing hydroxyl groups are hydroxyl alkyl esters, ⁇ -unsaturated carboxylic acids with primary or secondary hydroxyl groups, and mixtures of these esters with primary and secondary hydroxyl groups.
  • suitable hydroxyalkyl esters *, 3-unsaturated carboxylic acids with primary hydroxyl groups are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxibutyl acrylate, hydroxiamyl acrylate, hydroxylhexyl acrylate, hydroxioctyl acrylate and the corresponding methacrylates.
  • Examples of usable hydroxyalkyl esters with a secondary hydroxyl group are 2-hydroxypropyl acrylate, 2-hydroxibutyl acrylate, 3-hydroxibutyl acrylate and the corresponding methacrylates.
  • esters of other et,> -unsaturated carboxylic acids such as the crotonic acid and the isocrotonic acid are used.
  • component a 2 can be at least partially a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and an average of two moles. -Caprolactone.
  • a component of acrylic acid and / or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary ⁇ L carbon atom can also be used at least in part as component a_.
  • Glycidyl esters of strongly branched monocarboxylic acids are available under the trade name "Cardura”.
  • the implementation acrylic acid or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary carbon atom can take place before, during or after the polymerization reaction.
  • Suitable monomers containing epoxide groups are glycidyl esters of unsaturated carboxylic acids and / or glycidyl ethers of unsaturated compounds, such as e.g. Glycidyl (meth) acrylate, glycidyl ester of fumaric and maleic acid, glycidyl vinyl phthalate, glycidyl allyl phthalate and glycidyl allyl malonate.
  • Suitable monomers containing isocyanate groups are vinyl isocyanate, m-isopropenyl, eC -dimethylbenzyl isocyanate and isocyanatoalkyl esters of ot, ⁇ -unsaturated carboxylic acids of the general formula
  • Adducts of, for example, isophorone diisocyanate with hydroxyalkyl (meth) acrylates, such as e.g. Hydroxyethyl methacrylate can be used.
  • Component a 2 is used in an amount of 5 to
  • Component a is used in an amount of 40 to
  • Suitable compounds a_ are hydroxyalkyl esters, alkoxyalkyl esters, aryloxyalkyl esters, alkyl esters, and amides of unsaturated carboxylic acids and similar monomers.
  • alkyl esters such as methyl acrylate, ethyl acrylate * propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 3,5,5-trimethylhexyl acrylate, decyl acrylate, decyl acrylate , Hexadecyl acrylate, octadecyl acrylate, octa-decenyl acrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate,
  • monomers containing hydroxyl groups can also be used as component a ⁇ , such as, for example, the compounds already mentioned in the description of component a 2 .
  • component a is alkoxy and aryloxy alkyl esters, ⁇ _> unsaturated carboxylic acids, for example butoxyethyl acrylate and methacrylate, phenoxyethyl acrylate and methacrylate, acrylonitrile and methacrylonitrile.
  • unsaturated carboxylic acids for example butoxyethyl acrylate and methacrylate, phenoxyethyl acrylate and methacrylate, acrylonitrile and methacrylonitrile.
  • Total weight of the sum of components a to a. , component used a. is a monovinyl aromatic compound. It preferably contains 8 to 9 carbon atoms per molecule.
  • suitable compounds are styrene, vinyltoluenes, c (-methylstyrene, chlorostyrenes, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxistyrene, p-tert-butylstyrene, p Acetamidostyrene and m-vinylphenol, preferably vinyltoluenes and in particular styrene.
  • the polymerization reaction is carried out using polymerization initiators and, if appropriate, polymerization regulators.
  • Suitable free radical initiators are organic peroxides, e.g. Dibenzoyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, t-amylcumyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,2-di-tert-butylperoxibutane, tert-amylperbenzoate, 1, 3-bis (tert-butylperoxiisopropyl) benzene, diisopropylbenzene monohydroperoxide and diacyl peroxides, such as Diacetyl peroxide, peroxiketals, e.g.
  • thermolabile highly substituted ethane derivatives for example based on silyl-substituted ethane derivatives and based on benzpinacol.
  • thermolabile highly substituted ethane derivatives for example based on silyl-substituted ethane derivatives and based on benzpinacol.
  • aliphatic azo compounds such as azobiscyclohexanenitrile can also be used.
  • the amount of initiator is in most cases 0.1 to 5% by weight, based on the amount of monomers to be processed, but it can also be higher if necessary.
  • the initiator, dissolved in part of the solvent used for the polymerization, is gradually metered in during the polymerization reaction.
  • the reaction is preferably carried out in the presence of polymerization regulators in order to be able to better control the molecular weights or the molecular weight distribution.
  • Polymerization regulators are preferably suitable as regulators, with mercaptoethanol being particularly preferably used.
  • Other possible regulators are, for example, alkyl mercaptans, e.g. t-Dodecylmer-captan, octyl mercaptan, phenyl mercaptan, octyldecyl mercaptan, butyl mercaptan, thiocarboxylic acids, such as thioacetic acid or thiolactic acid.
  • t-dodecyl mercaptan is preferably used.
  • These regulators are used in an amount of up to 2% by weight, based on the amount of monomers to be processed. They are preferably dissolved in one of the monomer feeds and added with the monomers.
  • the polymerization is carried out in an organic solvent.
  • suitable solvents are alcohols, such as, for example, isobutanol, n-hexanol, 2-ethylhexanol, isooctyl alcohol, isononyl alcohol, isodecyl alcohol, isotridecyl alcohol, cyclohexanol, methylcyclohexanol, benzyl alcohol, methylbenzyl alcohol, tetrahydrofufuryl alcohol, 2,6-diacetone -Dimethyl-4-hexanol, 4-methyl-2-pentanol, tridecanol; Glycols and glycol derivatives, such as, for example, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, Hexylene glycol, 2-ethylhexanediol-1,3, diethylene glycol,
  • Triethylene glycol dipropylene glycol, methyl diglycol
  • phatic hydrocarbons such as various
  • Inert solvents such as aromatic and aliphatic hydrocarbons, esters or ethers are preferably used.
  • copolymers thus obtained are now further modified. If they contain neither anion-forming nor cation-forming groups, the copolymers are reacted with compounds a ⁇ .
  • Compounds a_ suitable are compounds with a number average molecular weight ⁇ 300 which have at least one anion- or cation-forming group and one group which is reactive with the functional groups of component a 2 .
  • component a is in amounts of 2 to 85 wt .-%, preferably 5 to 50 wt .-%, based on the weight of the copolymer obtained in the first stage.
  • the copolymer obtained in the first stage of the process contains, for example, hydroxyl groups
  • carboxylic acid anhydrides such as, for example, succinic anhydride, maleic anhydride, dodecenylsuccinic anhydride, hexa-hydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic acid, are used as component a ⁇ Half esterification react with the copolymer.
  • the copolymer obtained in this way is then modified further with the component to introduce the ethylenically unsaturated double bonds.
  • the copolymer obtained in the first stage of the process contains, for example, epoxy groups
  • it is advantageously first reacted with carboxyl group-containing ethylenically unsaturated compounds as component a g .
  • the hydroxyl group generated in this reaction can then be reacted by adding carboxylic acid anhydrides as component a 5 and the desired acid number of the polymer A can thus be set.
  • suitable monomers containing carboxyl groups and suitable carboxylic acid anhydrides are the compounds already listed.
  • Cation-forming groups can be introduced, for example, by aminolysis.
  • the double bonds are introduced into polymer A by reaction with component a g . If the copolymer obtained in the first stage already contains anion- or cation-forming groups, this copolymer obtained in the first stage is reacted directly with component a g .
  • Component a is used in an amount of 2 to
  • Compounds which are suitable as component a are compounds which, in addition to a group which is reactive with the anion- or cation-forming groups of component a or a, and / or the functional groups of the copolymer, also comprise at least one ethylenically unsaturated double bond and which have a number average molecular weight ⁇ 300.
  • copolymer prepared contains carboxyl groups
  • monomers which contain hydroxyl groups or epoxy groups for example, can be used as component a fi .
  • Suitable monomers containing epoxide and hydroxyl groups are the compounds already listed.
  • component a ß to the acrylate copolymer obtained can easily be carried out under reaction conditions known per se. Depending on the type of reaction (carboxy / epoxy; carboxy / hydroxy), the reaction takes place at temperatures of 80 to 150 ° C. If appropriate, a suitable catalyst can also be used, such as, for example, tertiary amines, triphenylphosphine, trialkylphosphites and chromium (III) octoate.
  • the catalyst is usually used in an amount of 0.01 to 0.5% by weight, based on the weight of the sum of components a. to a ß / used.
  • the reaction of component a ß with the acrylate copolymer advantageously takes place in the presence of a polymerization inhibitor or in the presence of suitable stabilizers in order to prevent thermal polymerization and thus gelation of the system during the reaction.
  • suitable polymerization inhibitors or stabilizers are hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, benzophenone, sterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol, phenothiazine, nitrobenzene, among others.
  • These inhibitors or Stabilizers are usually used in amounts of 0.001 to 0.5% by weight, preferably 0.01 to 0.1% by weight, in each case based on the
  • reaction of component ao with the acrylate copolymer usually takes place with inertization, for example by working in a nitrogen /
  • Air-atmosphere (mixing ratio 3: 1).
  • the unsaturated polymer A thus produced has a double bond equivalent of 1,500 to 10,000, preferably 2,000 to 5,000.
  • the double bond equivalent is the weight of the polymer A in g, which contains 1 mol of ethylenically unsaturated double bonds.
  • the number average molecular weight of the unsaturated polymer A is usually between 1,000 and 10,000, preferably between 2,000 and 5,000.
  • these unsaturated resins A have a dispersity between 2 and 15.
  • these unsaturated resins A contain 0.5 to 5.0 milliequivalents, preferably 1.25 to 2.32 milliequivalents, of anion or cation-forming groups per 1 g of resin. These groups are at least partially reacted with a Base or acid transferred to the charged groups.
  • the degree of neutralization of these groups is generally between 10 and 80%, preferably between 30 and 40%.
  • Preferred resins A are carboxyl-containing copolymers which have an acid number between 50 and
  • tertiary amines such as e.g. Triethylamine, alkali metal hydroxides such as sodium and potassium hydroxide, etc. used. These can be used individually or as a mixture of two or more bases.
  • Lactic acid, acetic acid, formic acid, phosphoric acid and the like are suitable for neutralizing basic groups. .
  • the unsaturated resin A is used in the coating compositions in an amount of 35 to 85% by weight, preferably 60 to 85% by weight, based in each case on the weight of the sum of components A to D.
  • the coating compositions advantageously also contain at least one monomeric ethylenically unsaturated compound B.
  • Compounds B with at least two ethylenically unsaturated double bonds per molecule are preferably used as component B.
  • This compound B is usually present in the coating agent in amounts of 0 to 60% by weight, preferably 10 to 35% by weight, based on the weight of the sum of components A to D. Examples of suitable monomeric compounds B are
  • Di- and poly (meth) acrylates e.g. 1,3-propanediol
  • Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and the triacrylate of alkoxylated trimethylolpropane are preferably used as compound B.
  • the coating compositions according to the invention contain as component C 1 to 10% by weight, preferably 2 to 7% by weight, based on the weight of the sum of components A to D, of at least one photoinitiator.
  • ketone-based initiators for example acetophenone, benzophenone, diethoxiacetophenone, m-chloroacetophenone, propiophenone, benzoin, benzil, benzil dimethyl ketal, anthraquinone, thioxanthone and thioxanthone derivatives as well as mixtures of different initiators.
  • ketone-based initiators for example acetophenone, benzophenone, diethoxiacetophenone, m-chloroacetophenone, propiophenone, benzoin, benzil, benzil dimethyl ketal, anthraquinone, thioxanthone and thioxanthone derivatives as well as mixtures of different initiators.
  • photoinitiators are described in EP-A-176 356.
  • aqueous coating compositions according to the invention can optionally also contain solvents in order to improve the flowability of the resin component.
  • solvents commonly used for this purpose are hydrophilic solvents, such as isopropanol, n-butanol, t-butanol, methoxiethanol, ethoxiethanol, butoxiethanol, diethylene glycol, methyl ether, dioxane and tetrahydrofuran.
  • the aqueous coating compositions can also comprise hydrophobic solvents, such as toluene, xylene and other aromatic hydrocarbons, and also methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and 2-ethylhexyl alcohol.
  • the amount of the organic solvent used as component E is generally between 0 and 30% by weight, preferably between 0 and 5% by weight, based on the weight of the sum of components A to D.
  • the coating compositions according to the invention may optionally also contain 0 to 10% by weight, preferably between 0 to 2% by weight, based on the weight of the sum of components A to D, of further auxiliaries and additives.
  • dyes, leveling and matting agents, complexing agents for copper ions and others can be added to the coating agents.
  • the aqueous coating agent is first deposited electrophoretically on the copper surface.
  • the bath concentration (as solids content) is usually 3 to 25% by weight, preferably 10 to 20% by weight.
  • the bath temperature is generally between 15 and 40 ° C, preferably between 25 and 30 ° C.
  • a copper-clad substrate made of insulating material is dipped into this coating bath set in this way and connected to a DC voltage source. Depending on the coating material used, this copper-clad substrate is switched as an anode or cathode.
  • the deposition voltage is generally between 50 and 500 V, the deposition time is generally between 30 s and 5 min.
  • the dry film layer thickness of the film obtained is generally between 10 and 35 .mu.m.
  • the choice of the deposition voltage and the deposition time depends not only on the size ratio of the anode to the cathode, their distance from one another, the flow conditions in the deposition vessel, the bath temperature and the bath solids content, but also on the desired layer thickness of the lacquer film and on the geometry of the substrate to be coated from. If three-dimensional molded parts are to be coated with a uniform layer thickness using the so-called wrap, ie rear and inner surfaces should also be coated this requires higher deposition tensions and longer deposition times than if only 2-dimensional molded parts are to be coated.
  • the coated product is led out of the electro-immersion bath and washed with water or with ultrafiltrate. Subsequently, the moisture contained in the deposited film is usually removed by heating to temperatures of 50 to 150 ° C. for a period of 3 to 30 minutes. 1
  • a mask is then placed on the uncured, photo-curable coating film obtained, which essentially consists of radiation-opaque and radiation-opaque. permeable surfaces. Then the loading takes place
  • the exposure can also take place by means of a computer-controlled laser beam without a mask.
  • the radiation used in the exposure according to the invention varies depending on the absorption of the photopolymerization initiator.
  • the wavelength of the radiation is usually in the range from 200 to 600 nm.
  • Suitable radiation sources are, for example, carbon arcs, mercury vapor lamps, tungsten lamps, 5 argon and xenon glow discharge lamps, photographic floodlights and fluorescent tubes with ultraviolet-emitting phosphors as well as eximer, argon and xenon fluoride Krypton fluoride laser.
  • mercury vapor lamps and metal halide lamps as well as lasers are particularly preferred in the case of 3-dimensional conductor tracks.
  • the exposure time is generally dependent on the type of radiation-sensitive resin used and on other factors, such as the thickness of the electrodeposited polymer layer and the selected photoinitiator, the type of radiation source and its distance from the film.
  • the respective radiation duration can easily be determined by routine tests. In order to be able to cure the films as economically as possible, however, it should be possible to achieve curing speeds which are as short as possible.
  • the film is developed with an aqueous solvent.
  • the radiation-polymerizable resin contains acidic groups
  • weakly alkaline aqueous solutions are used as the development solution, which bring about the water solubility of the unexposed parts by neutralizing the acidic groups in the film layer.
  • development solutions are aqueous, highly dilute sodium or potassium hydroxide solution, aqueous sodium or potassium hydrogen carbonate solutions, sodium or potassium carbonate solutions, aqueous ammonia or sodium hydrogen phosphate solutions.
  • the radiation-polymerizable resin contains basic groups
  • weakly acidic, aqueous solutions such as, for example, aqueous acetic acid, lactic acid, glycolic acid or p-toluenesulfonic acid, are used as developing solutions.
  • the further process step now depends on whether — as is customary with conventional printed circuit boards — the conductor tracks are produced by etching away excess copper or whether they are built up galvanically.
  • the printed circuit boards can be produced by removing the portion of the copper foil on the substrate which was revealed on the substrate by the development treatment, by means of an etching treatment with iron (III) chloride solution or ammonium perchlorate solution.
  • the radiation-cured film on the circuit pattern is then removed by treatment with a stronger solvent than the solvent used in the development, a printed circuit being formed on the substrate.
  • a solvent similar to that used in development can only be used under more severe conditions.
  • stripping process it is possible, for example, to use concentrated sodium or potassium hydroxide solution in the case of resins with acidic groups or concentrated acids, such as, for example, sulfuric acid, in the case of resins with basic groups.
  • Another possibility for producing the printed circuit boards is that after the development, further copper is electrodeposited on the exposed copper surfaces until the copper layer reaches a layer thickness of 30 to 35 ⁇ m. At this point in the reinforced copper layer, there are the conductor tracks later.
  • the polymerized film is then removed, as described above, by treatment with a stronger solvent or with a solvent similar to that used in developing, but under more stringent conditions.
  • the exposed metal is then - as also described above - etched away.
  • This method has the advantage that initially only a very thin copper layer of 0.5 to 5 ⁇ m has to be applied, which merely ensures that the substrate is coated with a conductive layer and thus electrophoretically with the resist. Material can be coated. In addition, considerably less copper has to be etched away in this process, which represents a further decisive advantage.
  • the polymers A were produced in a reactor with nitrogen supply, stirrer and metering devices.
  • the monomer composition of the polymers is given in Table 1.
  • All polymers are prepared with a nitrogen supply in xylene with 50% polymerization solids at a polymerization temperature of 110 ° C.
  • Azoisovaleronitrile is used as the initiator in an amount of 4%, based on the weight of the monomers.
  • Mercaptoethanol is used in each case as a regulator in an amount of 1%, based on the weight of the monomers.
  • the regulator is metered in together with the monomers over a period of 4 h.
  • the initiator is metered in in the form of a 10% solution in xylene over a separate feed over a period of 4.5 h.
  • the temperature is then kept at 110 ° C. until the theoretical solids content of 50% (20 min, 180 ° C.) is reached (approx. 3-4 h).
  • the subsequent modification of the polymer obtained with glycidyl methacrylate as component a ß is in an air atmosphere at a temperature of 90 ° C in the presence of 0.1% chromium octoate as a catalyst, 0.1% 2,6-di-tert-butyl-p cresol and 0.05% phenothiazine as polymerization inhibitors, all percentages being based on the weight of the monomers used, including glycidyl methacrylate.
  • the reaction is continued until the theoretical acid number is reached.
  • the xylene is then distilled off until a solids content of 70% (1 h, 130 ° C.) is reached. 1
  • the 70% solution of the polymer AI is partially neutralized with dimethylethanolamine.
  • the degree of neutralization (NG) is given in Table 1.
  • the remaining constituents of the coating composition (monomer B, photoinitiator C) are then added and then converted into a dispersion by slowly adding distilled water with stirring.
  • the composition of the resulting aqueous coating composition 1 is shown in Table 2.
  • the aqueous coating agent 1 was then 5 with constant stirring in the dark at 30 ° C for 7 days 5 to evaporate the volatile solvent components, such as. of the xylene, stirred before the deposits and tests were carried out.
  • the coating films are deposited at a bath temperature of 25 ° C. in a 3 1 vessel and with 2.5 1 bath liquid. For this purpose, cleaned and degreased copper laminates (immersed surface 230 cm) are switched and coated as an anode.
  • the separation conditions are chosen so that
  • the coated laminates are then dried in a forced air oven at 80 ° C. for 20 minutes. After storage for 24 hours at room temperature, the lacquer films are cured after being partially covered with a commercially available mask by irradiation using a medium-pressure mercury lamp (lamp power 80 W / cm). The distance between 1
  • Lamp and coated substrate is 25 cm.
  • the lamp is arranged perpendicular to the direction of transport.
  • the feed speed of the conveyor belt c is adjusted to values between 1 and 20 m / min.
  • the maximum feed rate at which it is ensured that the hardened films in the developing bath show no changes in the surface is shown in Table 3.
  • the unexposed parts of the lacquer film are removed by immersing the coated copper laminates in a 2% sodium carbonate solution.
  • the sodium carbonate solution has a temperature of 20 ° C. and is stirred at 200 revolutions / min.
  • the immersion time required to detach the unexposed parts is shown in Table 3.
  • the hardened parts of the paint film are removed by immersing the developed copper laminates in a 3% sodium hydroxide solution.
  • the sodium hydroxide solution has a temperature of 20 ° C and is stirred at 200 revolutions / min.
  • the immersion time required to detach the exposed parts is given in Table 3.
  • An aqueous coating agent 2 is produced analogously to Example 1, which differs from the aqueous coating agent 1 only in that instead of the solution of the polymer AI, the solution of the polymer A2 is now used.
  • the composition of this coating agent 2 is shown in Table 2.
  • the deposition of this aqueous coating agent 2 and the curing and testing of the resulting coating is carried out analogously to Example 1. The results are shown in Tables 2 and 3.
  • aqueous coating compositions VI to V4 are prepared which differ from the aqueous coating composition 1 only in that the solutions of the polymers AI to V4 are now used instead of the solution of the polymer AI.
  • the composition of these coating compositions VI to V4 is shown in Table 2.
  • Example 3 The deposition of these aqueous coating compositions VI to V4 and the curing and testing of the resulting coatings is carried out analogously to Example 1. The results are shown in Tables 2 and 3. Example 3
  • An aqueous coating agent 3 is prepared analogously to Example 2, which is made up of the aqueous coating
  • Layering agent 2 differs only in that instead of 3% trimethylolpropane triacrylate, 5% trimethylolpropane triacrylate, based in each case on the total weight of the aqueous coating agent, is used.
  • aqueous coating compositions V5 to V7 are produced which differ from the aqueous coating compositions V2 to V4 only in that instead of 3% trimethylolpropane triacrylate they now have 5% trimethylolpropane triacrylate, based in each case on the total weight of the aqueous coating agent.
  • Table 1 Composition and properties of the polymers AI, A2, VI, V2, V3 and V4
  • Table 2 Composition of the aqueous coating compositions and their deposition data
  • the break-off voltage which is often also referred to as breakdown voltage, is the upper limit of the bath voltage or separation voltage. At this or higher voltages, one or more of the following effects occur:
  • Table 4 Deposition data and test results of the coatings of example 3 and comparative examples V5 to V7
  • Comparative example V2 shows that the breaking tension can be increased by incorporating hexanediol dimethacrylate into the polymer.
  • Another disadvantage is that, despite the high acid number of the coating composition, the stripping time with 3% sodium hydroxide solution cannot be reduced to economical times.
  • the coating composition of Comparative Example 1 shows a breaking voltage of 300 V, so that a sufficient wrap can be achieved with this coating composition.
  • the remaining properties of the coating composition are completely inadequate for use as a photoresist material.
  • a feed rate of 1 m / min can be set in order to achieve sufficient curing.
  • Another disadvantage is that, despite the high acid number of the coating agent, the stripping time with 3% sodium hydroxide solution cannot be reduced to economical times of less than 10 minutes.
  • the coating compositions of Examples 1 and 2 are characterized by high tear-off tensions of 450 and
  • a glass fiber-reinforced epoxy resin laminate provided with a 3 to 5 .mu.m thick copper layer and usually used for the production of printed circuit boards is electrophoretically coated with the aqueous coating agent 2.
  • the separation conditions are:
  • Adhesive bath material was rinsed off with deionized water.
  • the coated laminate is then dried in a forced air oven at 80 ° C. for 10 minutes.
  • the coating is cured by irradiation using a mercury pressure lamp (radiation power 100 J / cm, measured on the surface of the paint).
  • the unexposed parts of the paint film in one suitable spray chamber detached by treatment with 3% sodium hydrogen carbonate solution.
  • the flanks of the remaining material are smooth and steep.
  • the exposed copper surfaces in ei ⁇ nem commercially available plating bath to be Schichts ⁇ strength of 30 / To enhanced without causing Beeaudi ⁇ conditions of the coating layer occur.
  • the exposed parts of the coating film are removed in a suitable spray chamber by treatment with 3% sodium hydroxide solution for 5 minutes.
  • the galvanically reinforced conductor tracks are then obtained by differential etching using a commercially available etching solution based on sulfuric acid.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
PCT/EP1991/000505 1990-03-24 1991-03-16 Wässrig entwickelbares, negativ wirkendes, elektrophoretisch abscheidbares und photohärtbares beschichtungsmittel sowie seine verwendung zur herstellung von leiterbahnen WO1991014972A1 (de)

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KR1019920702314A KR960014055B1 (ko) 1990-03-24 1991-03-16 물로 현상가능하고 음전기-작동성이며 전기이동적으로 침착가능하고 광경화성인 코팅제, 및 도체 트랙을 제조하기 위한 그것의 용도
BR919106275A BR9106275A (pt) 1990-03-24 1991-03-16 Agente de revestimento revelavel aquosamente,que atua negativamente,depositavel eletroforeticamente e fotoendurecivel,bem como sua aplicacao para a preparacao de vias de condutores
JP3506290A JPH087440B2 (ja) 1990-03-24 1991-03-16 水で現像可能で電着可能および光硬化可能なネガ型の被覆剤、印刷回路の製造法、ならびに２次元的、２１／２次元的および３次元的な導体板の製造法

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DE4009563A DE4009563A1 (de) 1990-03-24 1990-03-24 Waessrig entwickelbares, negativ wirkendes, elektrophoretisch abscheidbares und photohaertbares beschichtungsmittel sowie seine verwendung zur herstellung von leiterbahnen
DEP4009563.0 1990-03-24

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CA (1) CA2078682A1 (ja)
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WO (1) WO1991014972A1 (ja)

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JP3044689B2 (ja) * 1994-10-14 2000-05-22 日本ゼオン株式会社 感光性エラストマー組成物及び感光性ゴム版

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070258A (en) * 1976-05-24 1978-01-24 Scm Corporation Dual cure cathodic electrocoating compositions
US4105518A (en) * 1974-06-19 1978-08-08 Scm Corporation Ultraviolet curing of electrocoating compositions
EP0176356A2 (en) * 1984-09-26 1986-04-02 Rohm And Haas Company Photosensitive polymer compositions, electrophoretic deposition processes using same, and the use of same in forming films on substrates

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Publication number Priority date Publication date Assignee Title
JPH083634B2 (ja) * 1986-05-09 1996-01-17 関西ペイント株式会社 プリント配線フォトレジスト用電着塗料組成物の電着塗装方法
JPH0644150B2 (ja) * 1986-05-09 1994-06-08 関西ペイント株式会社 プリント配線フオトレジスト用電着塗料組成物
JPH01122189A (ja) * 1987-11-05 1989-05-15 Kansai Paint Co Ltd プリント配線板フォトレジスト用電着塗料組成物
JPH0769612B2 (ja) * 1988-03-28 1995-07-31 関西ペイント株式会社 プリント配線フオトレジスト用電着塗装方法
GB8827847D0 (en) * 1988-11-29 1988-12-29 Ciba Geigy Ag Method
JP2696419B2 (ja) * 1990-07-04 1998-01-14 日本石油株式会社 カチオン電着型ネガ型エッチングレジスト組成物
JPH04116181A (ja) * 1990-09-03 1992-04-16 Nippon Oil Co Ltd カチオン電着型ネガ型エッチングレジスト組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105518A (en) * 1974-06-19 1978-08-08 Scm Corporation Ultraviolet curing of electrocoating compositions
US4070258A (en) * 1976-05-24 1978-01-24 Scm Corporation Dual cure cathodic electrocoating compositions
EP0176356A2 (en) * 1984-09-26 1986-04-02 Rohm And Haas Company Photosensitive polymer compositions, electrophoretic deposition processes using same, and the use of same in forming films on substrates

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KR937000609A (ko) 1993-03-15
KR960014055B1 (ko) 1996-10-11
EP0521935A1 (de) 1993-01-13
CA2078682A1 (en) 1991-09-25
JPH05502518A (ja) 1993-04-28
DE4009563A1 (de) 1991-09-26
BR9106275A (pt) 1993-04-13
JPH087440B2 (ja) 1996-01-29

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