JPH087440B2 - Water-developable, electrodepositable and photocurable negative type coating, method for producing printed circuit, and method for producing two-dimensional, two-dimensional and three-dimensional conductor plates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The subject matter of the present invention is: A) 35-85% by weight of at least one ethylenically unsaturated, water-dispersible or water-soluble polymer, B) at least one ethylenically unsaturated monomer. -60% by weight, C) 1-10% by weight of at least one photoinitiator, D) 0-10% by weight of auxiliaries and additives and E) optionally containing organic solvents dispersed in water, developable Negative electrodepositable and photocurable water-based coatings, the total content of components A to D being 100% by weight in each case.

The invention also relates to the use of said coating for the production of conductive paths.

In the manufacture of electronic devices, conductor plates have a significant significance. Conventional conductor plates are made of glass fiber-
Based on an epoxide laminate or another laminate. The function of the conductor plate is firstly a two-dimensional support that is flat and a coupling for the individual electronic components, such as capacitors, transistors and resistors. Separate electrical and structural elements are required to electrically and mechanically couple the conductor plate to the rest of the device.

A two-dimensional conductor plate of this kind is obtained, for example, by electrophoretically depositing a photocurable lacquer film on a copper plating layer and exposing it through a mask. Thereafter, the printed circuit pattern is developed by dissolving unexposed areas in the case of a negative photoresist material, and in the case of a positive photoresist material,
It is developed by dissolving the exposed areas. The exposed copper surface is then removed by treatment with an acid etching solution. The printed circuit is subsequently obtained by removing the remaining lacquer layer.

A method of this kind for producing a two-dimensional conductor plate while using a water-developable, electrodepositable and photocurable negative resist material is described, for example, in EP 176356. ing. As the resist material, preferably an unsaturated polymer having a carrier group, an acid or base for neutralizing the carrier group, a photoinitiator and an aqueous solution or emulsion of an unsaturated crosslinkable monomer is used. To be done. Examples of suitable polymers include linear acrylate polymers, vinyl polymers, epoxy resins, polyurethanes and polyesters.

When the photoresist material is deposited on the anode, the problem arises that the copper connected as the anode is partially oxidized to Cu (II) ions. This copper ion diffuses into the deposited resist film and forms a complex with a carboxyl group, a thio group, etc. This complex impairs the developability of the resist material and leads to a residual layer on the substrate. . This effect occurs strongly as the deposition voltage of the resist material increases, and causes serious problems, especially in the vicinity of the so-called breakdown voltage of the material to be deposited.

In the case of the method described in DE 3715412 A1, this problem is solved by adding to the photoresist material a chelating reagent for copper ions. Furthermore, the photoresist material described in this German patent application 3715412 discloses a water-soluble or water-soluble polymer having an acid value of 20 to 300, an unsaturated equivalent of 150 to 300 and a number average molecular weight of 300 or more. It contains a dispersible polymerizable unsaturated resin, optionally an unsaturated monomeric compound and a water-insoluble photopolymerization initiator. Examples of unsaturated resins include, inter alia, reaction products of a carboxyl group-containing linear acrylate and a glycidyl group-containing unsaturated compound, and reaction products of a hydroxyl group-containing linear acrylate and an isocyanate group-containing unsaturated compound.

However, the photoresist material described in DE 3715412 A1 has a deposition voltage achievable in order to achieve a sufficiently high dry coating layer thickness (230 μm), due to the low breakdown voltage of the material. It has the disadvantage of having a significantly lower value. Consequently, the material necessarily exhibits only poor hugging or wrapping.

A further development of the conductor plate to date is 2 1/2
It is a three-dimensional and three-dimensional conductor plate. This type of conductor plate is a member made of a thermoplastic and manufactured by an injection molding method, and this member is selectively metallized. Functionally the following are equated: conductor plates, plug connectors, "chip carriers" and mechanical and structural elements. The accuracy and reproducibility from one member to another is outstanding because the shapes, sections, holes, etc. of the members are present in the precision injection mold.

In order to ensure a uniform coating of the three-dimensional molded part with the photoresist material, that is to say a uniform coating of the surfaces present, for example, behind and inside the through-holes, a high deposition voltage of the photoresist material (generally depending on the molded part) 250-300
V) is required. This is because only in this case can a good hug or winding be obtained. In order to be able to work with high deposition voltages in this way, the photoresist material used must have a breakdown voltage of at least 300-350 V, depending on the molding.

Finally, from the description of U.S. Pat.
Anodically depositable and photocurable coating materials based on linear or branched unsaturated acrylate polymers having an average molecular weight of ˜100,000 are known. The coating materials described in this publication give coatings with high hardness and good solvent resistance. However, the use or suitability of the coating material as a photoresist material is described in US Pat.
No description is given in the 925 specification.

Further, from the description of U.S. Pat.
Cathode-depositable, photocurable coating materials based on linear or branched unsaturated acrylate polymers having an average molecular weight of 100000 are known. The use or suitability of the coating material as a photoresist material is likewise not described.

The object of the present invention is therefore the development of water-, electrodeposition- and photo-curable negatives, which have a breakdown voltage as high as possible of at least 300-350 V and have a good hugging or winding behavior, depending on the molding. A type of photoresist material is provided. Furthermore, this photoresist material must cure as quickly as possible, and rapid strippability and developability if it is simultaneously well stable to commonly used corrosion and electroplating baths. Must be shown.

This problem is surprisingly because A) at least one ethylenically unsaturated water-dispersible or water-soluble polymer 35-85% by weight, B) at least one ethylenically unsaturated monomer 0-60% by weight. , C) at least one photoinitiator 1-10% by weight, D) auxiliaries and additives 0-10% by weight and E) optionally containing an organic solvent dispersed in water (provided that components A-D are present). The sum of the weight content of each is 10
0% by weight), water-developable, electrodepositable and photocurable negative type coatings, wherein the coatings have a double bond equivalent of polymer A of 1500 to 10000 and 0.5 Having an anion or cation forming group content of ˜5.0 meq and I. In the first step, a ₁ ) at least 2 ethylenically unsaturated polymerizable double bonds and number average molecular weight per molecule <At least one monomer from 5 to 30 wt% with a 400, a ₂₎ at least one ethylenically unsaturated copolymerizable with at least one anion or cation forming group and / or at least one functional group 5-30 monomers
%, A ₃ ) 40-80% by weight of at least one other ethylenically unsaturated copolymerizable monomer without anion or cation-forming groups, excluding vinyl aromatic hydrocarbons, a ₄ ) at least 1 to 50% by weight of one vinyl aromatic hydrocarbon (however, the sum of the weight contents of the components a _{1 to} a ₄ is 100 in each case)
% By weight), II. If the copolymer obtained in the first step does not contain anion-forming groups or cation-forming groups, the obtained copolymer is obtained. the functional groups relative to the total weight of a ₅₎ component a ₁ ~a _4, having at least one anion or cation-forming groups and copolymers of groups capable of reacting with the functional group and a number average molecular weight <300 at least partially reacted least one compound 2-85 wt% and, III. the copolymer a ₆₎ at least one ethylenically unsaturated double bond and an anion or cation component a ₂ or a ₅ At least one compound 2-2 having a group capable of reacting with ion-forming groups and / or functional groups of the copolymer and having a number average molecular weight <300
0% by weight (based on the total weight of components a _{1 to} a ₄ ),
And IV. Is characterized in that it can be prepared by at least partially neutralizing the anion- or cation-forming groups of the resulting copolymer.

Furthermore, the subject of the invention is one method for producing printed circuits, in which the coating according to the invention is electrophoretically deposited on the copper surface and the polymer image is produced by irradiation and development. can get. Furthermore, the invention relates to the use of the coating as a photoresist material for producing two-dimensional, 21 / 2-dimensional and three-dimensional conductive paths.

Surprisingly, this coating material exhibits a high breakdown voltage of at least 300-350 V and a good hugging or wrapping behavior, depending on the molded part to be coated, in which case it cures very quickly at the same time as well as good. It was unexpected to show rapid strippability and developability at. When the coating agent according to the invention is used, in particular 2
Half-dimensional and three-dimensional conductive paths, as well as two-dimensional conductive paths, can be produced by simple and economical methods.
This high breakdown voltage inevitably allows the coating to work with a relatively high deposition voltage, which achieves a uniform layer thickness both on the surface remote from the electrodes and in the voids. Is important to do. However, nevertheless, this required deposition voltage has a sufficient distance to the breakdown voltage, so that in the case of anodic deposition, the problems due to the oxidation of copper ions are sufficiently avoided. .

By the way, first, a compound suitable for producing an unsaturated polymer will be described in detail.

Polymerizable unsaturated resin A used according to the invention
Is generally 70-200 ° C., preferably 100-200, of monomers a _{1 to} a ₄ per difference.
It can be produced by obtaining a copolymer by radical solution polymerization at a temperature of up to 150 ° C.

Examples of suitable monomers a ₁ having at least two ethylenically unsaturated polymerizable double bonds per molecule and having a number average molecular weight of less than 400 are represented by the general formula: [Wherein, R is H or CH ₃ , X is O, NR ′, S, provided that R ′ is H, alkyl,
Aryl, and n is 2 to 12], [Wherein, R ¹ and R ² are H, —CH ₃ , —CH ₂ —CH ₃ , and —CH ₂ —CH (CH ₃ ) ₂ and X is O, NR ′, S, provided that R is ′ Is H, alkyl,
Aryl, m is 1-2], ₂ -CH ₂ -X- (III) wherein _{-X-CH 2 -S-CH,} X is O, NR ', S, and Here, R ′ Is H, alkyl,
Aryl], [Wherein, X is O, NR ', S, provided that R'is H, alkyl,
Aryl], [Wherein, X is O, NR ', S, provided that R'is H, alkyl,
Aryl], [Wherein R is alkyl or aryl, X is O, NR ', or S, provided that R'is H, alkyl,
It is an aryl].

Examples of compounds of this type are hexanediol diacrylate, hexanediol dimethacrylate, glycol diacrylate, glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate. Furthermore, divinyl compounds such as, for example, divinyl benzene, are also suitable as component a ₁ . Of course, a mixture of polyfunctional monomers may be used.

Further, the component a ₁ may be a reaction product of a carboxylic acid having a polymerizable olefinic unsaturated double bond and glycidyl acrylate and / or glycidyl methacrylate. Further, the component a ₁ is 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. Can be

Furthermore, as component a ₁ , acrylic or methacrylic acid 2
Moles with bisphenol-A- or bisphenol-
Reaction products with 1 mol of F-diglycidyl ether are also suitable. Alkoxylated bisphenol-A- or bisphenol-F-di (meth) acrylate may be used as component a ₁ .

Further, as the component a _1, it is also possible to use a reaction product of a polyisocyanate and an unsaturated alcohol or amine containing a polymerizable double bond. An example of this is the reaction product of 1 mol of hexamethylene diisocyanate and 2 mol of allyl alcohol.

Preferred component a ₁ is a compound having at least 2 methacryloyl groups per molecule.

The component a ₁ is 5 to 30 relative to the total weight of the components a _{1 to} a _4.
It is used in an amount of 10% by weight, preferably 10-20% by weight.

As component a ₂ , a monomer having an anion or cation forming group is advantageously used.

Examples of suitable monomers having anion-forming groups are carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and dimethylacrylic acid and succinic acid mono (meth). ) Acryloyloxyethyl ester, phthalic acid mono (meth) acryloyloxyethyl ester and phthalic anhydride or succinic anhydride, for example, Union Carbide trade name TONE M100
Reaction products with hydroxyalkyl (meth) acrylate / ε-caprolactam adducts such as those commercially available at. Also suitable are phosphoric acid derivatives and phosphoric acid derivatives, for example hydroxyalkyl (meth) acrylate phosphoric acid monoesters and hydroxyalkyl (meth) acrylate sulfuric acid monoesters. Advantageously, acrylic acid and methacrylic acid are used.

Further suitable as component a ₂ are monomers capable of forming cations, eg quaternary ammonium groups, sulfonium groups or sulfoxonium groups. An amino group-containing monomer is preferably used as the cation-forming monomer a ₂ . Examples of suitable amino group-containing monomers a ₂ are N, N-
Dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N-2-
Tert-butylaminoethyl (meth) acrylate, N, N-
Dimethylaminopropyl (meth) acrylamide and p-dimethylaminostyrene.

However, it is also possible to use monomers which do not actually have anion or cation-forming groups, but which have other functional groups, for example hydroxyl groups, epoxy groups or isocyanate groups.

Examples of suitable hydroxyl group-containing monomers a ₂ are hydroxyalkyl esters of α, β-unsaturated carboxylic acids having primary or secondary hydroxyl groups as well as those having primary or secondary hydroxyl groups. It is a mixture of esters. Examples of suitable hydroxyalkyl esters of α, β-unsaturated carboxylic acids having primary hydroxyl groups are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and correspondingly. It is a methacrylate. Examples of usable hydroxyalkyl esters having a secondary hydroxy group include:
Mention may be made of 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.

Of course, it is also possible to use different α, β-unsaturated carboxylic acids, for example the corresponding esters of crotonic acid and isocrotonic acid.

Advantageously, component a ₂ may be the reaction product of at least partly 1 mol of hydroxyethyl acrylate and / or hydroxyethyl methacrylate with an average of 2 mol of ε-caprolactone.

As the component a _2, it is also possible to use the reaction product of at least partially acrylic acid and / or methacrylic acid with a glycidyl ester of a carboxylic acid having a tertiary α-carbon atom. The strongly branched monocarboxylic acid glycidyl ester is available under the tradename "Cardura". The reaction of acrylic acid or methacrylic acid with the glycidyl ester of a carboxylic acid having a tertiary α-carbon atom can be carried out before, during or after the polymerization reaction.

Examples of suitable epoxy group-containing monomers are glycidyl esters of unsaturated carboxylic acids and / or glycidyl ethers of unsaturated compounds, such as glycidyl (meth) acrylate, glycidyl esters of fumaric acid and maleic acid, glycidyl vinyl phthalate, glycidyl. Allyl phthalate and glycidyl allyl malonate.

Examples of suitable isocyanate group-containing monomers include vinyl isocyanate, m-isopropenyl-α, α'-dimethylbenzyl isocyanate and the general formula: [Wherein R represents H, CH ₃ , C ₂ H ₅ and X represents (CH ₂ ) n, where n is 1 to 12]. Isocyanate alkyl ester.

Also, for example, an adduct of isophorone diisocyanate with hydroxyalkyl (meth) acrylate, such as hydroxyethyl methacrylate, may be used.

The component a ₂ is 5 to 30 relative to the total weight of the components a _{1 to} a _4.
It is used in an amount of 10% by weight, preferably 10-20% by weight.

Ingredient ₃ is 40 to 80 relative to the total weight of ingredients a _{1 to} a _4.
It is used in an amount of% by weight, preferably 40-60% by weight. Examples of suitable compounds a ₃ are hydroxyalkyl esters, alkoxyalkyl esters, aryloxyalkyl esters, alkyl esters and amides α, β-unsaturated carboxylic acids and similar monomers.

Thus, for example, 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, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, octadecenyl acrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, Decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate and maleic acid, fumaric acid, crotonic acid and isocrotonic acid phases The esters may be used.

However, it is also possible to use, as component a ₃ , for example hydroxyl-containing monomers such as the compounds mentioned in the description of component a ₂ .

Also suitable as component a ₃ are alkoxyalkyl esters and aryloxyalkyl esters of α, β-unsaturated carboxylic acids, such as butoxyethyl acrylate and butoxyethyl methacrylate, phenoxyethyl acrylate and phenoxyethyl methacrylate, acrylonitrile and methacrylonitrile. Is.

Component a ₄ to the total weight of the sum of components a ₁ ~a ₄ is used in an amount of 0 to 50% by weight is a monovinyl aromatic compound. Advantageously, this compound contains 8 to 9 C per molecule.
Have atoms. Examples of suitable compounds are styrene, vinyltoluol, α-methylstyrene, chlorostyrene, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxystyrene, p-tert-butylstyrene. , P-acetamidostyrene and m-vinylphenol. Preference is given to using vinyltoluol and especially styrene.

The polymerization reaction is carried out using a polymerization initiator and optionally a polymerization modifier.

Suitable radical initiators are organic peroxides such as dibenzoyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, t-amyl milk peroxide, cumol hydroperoxide, di-tert-butyl peroxide, tert-butyl. Hydroperoxide, 2,2-di-tert-butylperoxybutane, tert-amyl perbenzoate, 1,3-
Bis (tert-butylperoxyisopropyl) -benzol, diisopropylbenzol monohydroperoxide and diacyl peroxides such as diacetyl peroxide, peroxyketals such as 2,2-di- (tertiary amylperoxy) -propane and ethyl-3,3- The-
(Tertiary amyl peroxy) -butyrate, thermally labile highly substituted ethane derivatives such as those based on silyl substituted ethane derivatives and those based on benzpinacol. Furthermore, an aliphatic azo compound,
For example, azobiscyclohexanenitrile may be used.

The amount of initiator is often 0.1 to 5% by weight, based on the amount of monomer to be processed, but in some cases even higher. The initiator dissolved in a part of the solvent used for the polymerization is gradually supplied during the polymerization reaction.
Advantageously, the initiator feed lasts longer than the monomer feed for approximately 1 to 2 hours, so that a good effect can be achieved during the post-polymerization stage. If the initiator is used under the reaction conditions with only a small decomposition rate, it can also be charged in whole or in part.

Advantageously, the reaction is carried out in the presence of a polymerization modifier, so that the molecular weight or the molecular weight distribution can be well controlled. Suitable regulators are in particular mercapto compounds, in which case mercaptoethanol is particularly preferably used. Further possible regulators are, for example, alkyl mercaptans, such as t-dodecyl mercaptan,
Octyl mercaptan, phenyl mercaptan, octyl decyl mercaptan, butyl mercaptan, thiocarboxylic acids such as thioacetic acid or thiolactic acid. It should be noted that in the case of the anhydride-functional comonomers, the modifier cannot react with the cyclic anhydride groups or can react with the cyclic anhydride groups only in very small amounts.
In this case, t-dodecyl mercaptan is preferably used. This modifier is 2 relative to the amount of monomer to be processed.
Used in amounts up to wt%. In particular, this modifier is dissolved in one of the monomer feeds and added together with the monomer.

 The polymerization is carried out in an organic solvent. Examples of suitable solvents
Is an alcohol such as isobutanol, n-hexano
, 2-ethylhexanol, isooctyl alcohol
Le, isononyl alcohol, isodecyl alcohol, a
Sotridecyl alcohol, cyclohexanol, matyl
Cyclohexanol, benzyl alcohol, methylben
Dil alcohol, tetrahydrofurfuryl alcohol,
Diacetone alcohol, 2,6-dimethyl-4-heptano
, 4-methyl-2-pentanol, tridecanoe
Glycols and glycol derivatives such as ethyl
Glycol, 1,2-propylene glycol, 1,3-butyl
Lenglycol, butanediol-1,4, hexlength
Recall, 2-ethylhexanediol 1,3, diethyl
Glycol, triethylene glycol, dipropylene
Glycol, methyldiglycol, ethyldiglycol
Ru, butyl diglycol, hexyl diglycol, tri
Propylene glycol methyl ether, methoxy trig
Recall, ethyl glycol acetate, butyl glyco
Acetate, ethyl diglycol acetate, ethi
Lenglycol diacetate; substituted aromatic compounds, eg
Xylol, Toluol, Solvent naphtha (Solven
t Naphtha ), Sulfur benzene, various Solvesso (S
olvesso ) Types, various shellsols ) Type
And Deasol ) And aliphatic hydrocarbons
And cycloaliphatic hydrocarbons such as various white spirits
With mineral oil, mineral turpentine, tetralin and decalin
is there. Advantageously, inert solvents such as aromatic hydrocarbons and
And aliphatic hydrocarbons, esters or ethers are used
Be done.

By the way, the copolymer thus obtained is further modified. When this copolymer has neither an anion-forming group nor a cation-forming group, the reaction between the copolymer and compound a ₅ is carried out. Suitable components a ₅ are compounds having at least one anion-forming group or cation-forming group and having groups capable of reacting with the functional groups of component a ₂ and having a number average molecular weight <300.

In this case, these anion-forming groups or cation-forming groups are introduced by reaction of the copolymer obtained in the first step with component a _5, and the product thus obtained is then mixed with component a ₆ The reaction can be further modified.
However, it is also possible for the copolymer obtained in the first step to be reacted with component a ₆ per unit and the product obtained can then be further modified by reaction with component a ₅ .

Component a ₅ is 2-85 relative to the total weight of the sum of components a ₁ ~a ₄
%, Preferably 5 to 50% by weight.

If the copolymer obtained in the first step of the process has, for example, a hydroxyl group, it is preferably used as component a ₅ as a carboxylic acid anhydride, such as succinic anhydride, maleic anhydride, dodecenyl succinic anhydride, Hexahydrophthalic anhydride,
Tetrahydrophthalic anhydride, phthalic anhydride, is used, which reacts with the copolymer under half-esterification. The copolymer thus obtained is then further modified with component a ₆ due to the introduction of ethylenically unsaturated double bonds.

When the copolymer obtained in the first step of the present method has, for example, an epoxy group, it is preferably reacted with a carboxyl group-containing ethylenically unsaturated compound as the component a ₆ per difference. Then, the hydroxyl groups generated during the reaction can be regulated can be reacted by the addition of a carboxylic acid anhydride as component a _5, thus the desired acid value of the polymer A. Examples of suitable carboxyl group-containing monomers as well as suitable carboxylic acid anhydrides are the compounds already mentioned.

Cation-forming groups can be introduced, for example, by aminolysis.

The double bond is introduced into the polymer A by the reaction with the component a ₆ . If the copolymer obtained in the first step already has an anion-forming group or a cation-forming group, the copolymer obtained in this first step is reacted directly with component a ₆ .

Component a ₆ is 2 to 20 relative to the total weight of the components a _{1 to} a _4.
%, Preferably 2 to 10% by weight.

Component a ₆ contains at least one ethylenically unsaturated double bond together with a group capable of reacting with the anion-forming group or cation-forming group of component a ₂ or a ₅ and / or the functional group of the copolymer. And compounds having a number average molecular weight <300 are suitable.

When the obtained copolymer has a carboxyl group, as the component a ₆ , for example, a hydroxyl group-containing or epoxy group-containing monomer can be used.

Examples of suitable epoxy group-containing and hydroxyl group-containing monomers are the compounds already mentioned.

The addition reaction of the component a ₆ to the obtained acrylate copolymer can be easily carried out under reaction conditions known per se. Kind of reaction (carboxy / epoxy; carboxy /
Depending on the (hydroxy), the reaction is carried out at 80-150 ° C. In some cases, a suitable catalyst, such as a tertiary amine,
Triphenylphosphine, trialkylphosphite and chromium (III) octenoate can be used together.

In this case, the catalyst is usually used in an amount of 0.01 to 0.5% by weight, based on the total weight of the components a _{1 to} a ₄ .

Reaction of the components a ₆ and acrylate copolymer is advantageously conducted in the presence of a presence or a suitable stabilizer polymerization inhibitors, thus the thermal polymerization, thus gelation of the system is prevented during the reaction It Examples of suitable polymerization inhibitors or stabilizers are hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, benzophenone, sterically hindered phenols such as 2,6-di-tert-butyl-p-cresol,
Examples include phenothiazine and nitrobenzol. These inhibitors or stabilizers are used in amounts of 0.001 to 0.5% by weight, preferably 0.01 to 0.1% by weight, based on the total weight of the components a _{1 to} a ₆ , respectively.

The reaction of component a ₆ with an acrylate copolymer is usually carried out under deactivation, for example in a nitrogen / air atmosphere (mixing ratio 3: 1).
It is done by the work inside.

The polymer A thus obtained is 1500 to 10000, preferably 2
It has a double bond equivalent weight of 000-5000. In this case, the double bond equivalent weight is the weight of polymer A in g containing 1 mol of ethylenically unsaturated double bonds. The number average molecular weight of the unsaturated polymer A is usually between 1000 and 10000, preferably 2000 to 5
Between 000. Generally, the unsaturated resin A has a dispersity of 2 to 15. The unsaturated resin A has an anion-forming group or a cation-forming group of 0.5 to 5.0 meq, preferably 1.25 g / g of the resin in order to achieve water solubility or water dispersibility.
Contains ~ 2.32 meq. These groups are converted to loading groups by at least partial reaction with bases or acids. The degree of neutralization of this group is generally between 10 and 80%, preferably between 30 and 40%.

A preferred resin A has an acid value of KOH of 50 to 200 mg / g, preferably KOH7.
A carboxyl group-containing copolymer having 0 to 130 mg / g.

To neutralize the carboxyl groups, usually tertiary amines such as triethylamine, alkali metal hydroxides,
For example, sodium hydroxide and potassium hydroxide are used. These can be used alone or 2
It can also be used as a mixture of one or more bases.

Suitable for neutralizing basic groups are lactic acid, acetic acid, formic acid, phosphoric acid and the like.

The unsaturated resin A is contained in the coating material in an amount of 35 to 85% by weight, preferably 60 to 85% by weight, based on the total weight of the components A to D.
Used in an amount of.

Preferably, the coating agent, in addition to the ethylenically unsaturated polymer A, still contains at least one monomeric ethylenically unsaturated compound B. Preference is given to using as component B compounds having at least two ethylenically unsaturated double bonds per molecule. Compound B is usually contained in the coating composition in an amount of 0 to 60% by weight, preferably 10 to 35% by weight, based on the total weight of components A to D.

Examples of suitable monomer compounds are di (meth) acrylates and poly (meth) acrylates such as 1,3-propanediol di (meth) acrylate, 1,2-propanediol di (meth) acrylate, 1,3 -Butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-butene-1,4-diol di (meth) acrylate, butylene glycol di (meth) acrylate, pentanediol di (meth) acrylate ,
Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2,2-dimethyl-1,3-propanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, decamethylene glycol di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate , Trimethylolethanedi (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, glycerin di (meth) acrylate, polyoxypropyl trimethylolpropane tri ( Meth) acrylate, pentaerythritol di (meth) acrylate,
Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,2,4-butanetriol di (meth) acrylate and, for example, alkyl (meth) acrylate ) Acrylate, crotyl (meth) acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, N-vinylpyrrolidone, isobornyl acrylate, vinyltoluol, styrene, polyfunctional (meth)
For example, acrylamide.

Preference is given to using as compound B hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and alkoxylated trimethylolpropane triacrylate.

The coating composition according to the invention contains component A in order to accelerate the curing.
To at least one photoinitiator 1 relative to the total weight of
-10% by weight, preferably 2-7% by weight, as component C. Usually, ketone-based initiators such as acetophenone, benzophenone, diethoxyacetophenone,
Mixtures of m-chloroacetophenone, propiophenone, benzoin, benzyl, benzyldimethylketal, anthraquinone, thioxanthone and thioxanthone derivatives and various initiators are used. Further suitable photoinitiators are described in EP-A-176356.

The aqueous coating composition according to the invention can optionally also contain a solvent, in order to improve the fluidity of the resin component. Examples of solvents commonly used for this purpose are hydrophilic solvents such as isopropanol, n-butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol, methyl ether, dioxane and tetrahydrofuran. In some cases, the aqueous coating may contain hydrophobic solvents such as toluene, xylol and other aromatic hydrocarbons and methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and 2-ethylhexyl alcohol. The amount of organic solvent used as component E is generally between 0 and 30% by weight, preferably between 0 and 5% by weight, based on the total weight of components A to D.

Finally, the coating materials according to the invention may optionally contain further auxiliaries and additives in an amount of 0 to 10% by weight, preferably 0 to 2% by weight, based on the total weight of components A to D. it can. For example, colorants, leveling and matting agents, complexing agents for copper ions, and the like can be added to the coating.

For the production of printed circuits, a water-based coating composition is electrophoretically deposited on the copper surface. The bath concentration (as solids content) is generally 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. In the coating bath thus prepared, a copper-plated substrate made of an insulating material is dipped and connected to a DC voltage source. In this case, depending on the coating material used, this copper-plated substrate is connected as an anode or cathode. The deposition voltage is generally between 50 and 500V,
The deposition time is generally between 30 s and 5 min. The dry coating layer thickness of the resulting coating is generally between 10 and 35 μm.

In this case, the deposition voltage and the deposition time are determined by the ratio of the size of the anode and the cathode, the distance between the anode and the cathode, the ratio of the current in the deposition vessel, the bath temperature and the desired layer thickness of the lacquer coating along with the bath solids. As well as the geometry of the substrate to be coated. In the case of coating a three-dimensional molded member with a uniform layer thickness while utilizing so-called hugging or wrapping, that is, in the case of coating the back surface and the surface existing on the inner side, it is more than the case of coating only the two-dimensional molded member. Also requires high deposition voltage and long deposition time. Therefore, above all, 2
The production of 1 / 2-dimensional and 3-dimensional conductor plates requires working with the highest possible deposition voltage, thus over the entire covering surface, for example in bores, in recesses and also from counter electrodes. Good hugging or wrapping at remote locations is ensured and thus a uniform layer thickness formation. Normal,
In this case, a deposition voltage of 250 to 500 V, preferably 300 to 450 V is used. At the same time, however, it should be noted that the deposition voltage is at least 50V under breakdown voltage. That is, when working near the breakdown voltage, the oxidation of copper to copper (II) ions doubles during precipitation at the anode. Furthermore, copper (II) ions diffuse into the deposited resist coating and form complexes with carboxyl groups, thio groups, etc., which on one side impair the developability of the resist material, A resist layer is formed on the face substrate.

After electrodeposition, the coated product is removed from the electrodeposition bath,
And washed with water or ultrafiltrate. Continued, usually,
Moisture contained in the deposited film is 50-150 ℃
Is removed by heating for 3 to 30 minutes.

Furthermore, on the obtained uncured photocurable coating film,
A mask is placed which consists essentially of radiopaque and radiolucent surfaces. After that, irradiation through this mask is performed. However, the exposure can also be performed without a mask by computer-controlled laser light.

The radiation used during the exposure according to the invention is varied depending on the photoinitiator. Usually the wavelength of radiation is
It is in the range of 200 to 600 nm. Suitable radiation sources are, for example, carbon arcs, mercury vapor lamps, tungsten lamps, argon glue discharge lamps and xenon glue discharge lamps, photographic floodlights and arc tubes with UV-emitting phosphors and excimer lasers, argon lasers, fluorides. A xenon laser and a krypton fluoride laser. Among these radiation sources, lasers are particularly advantageous, especially in the case of mercury vapor lamps and metal halide lamps and three-dimensional conductive paths.

The exposure time generally depends on the type of radiation sensitive resin used and other factors such as the thickness of the electrodeposited polymer layer and the selected photoinitiator, the type of radiation source and the radiation source and coating. Depends on distance. The respective irradiation time can be easily measured by ordinary tests. However, in order to be able to cure the coating as economically as possible, it is possible to achieve a curing rate as short as possible.

After irradiation, the part of the coating that was not exposed to the radiation is removed. To that end, the coating is developed with an aqueous solvent. When the radiation-polymerizable resin has an acid group, a weakly alkaline aqueous solution is used as the developing solution.
Neutralization of acid groups in the coating layer causes water solubility in the unexposed areas. Examples of such developing solutions are strongly diluted aqueous caustic soda solution or potassium hydroxide solution, aqueous sodium hydrogen carbonate solution or potassium hydrogen carbonate solution, sodium carbonate solution or potassium carbonate solution, aqueous ammonia solution or aqueous disodium hydrogen phosphate solution. On the other hand, when the radiation-polymerizable resin has a basic group, a weakly acidic aqueous solution such as an acetic acid aqueous solution, a lactic acid aqueous solution, a glycolic acid aqueous solution or a p-toluolsulfonic acid aqueous solution is used as the developer. It

Furthermore, other processing steps depend on whether the conductive paths are produced by corroding excess copper or by electroplating, as is customary, for example, on conventional conductor plates.

The conductor plate can be manufactured by removing the copper foil portion exposed on the substrate by the development treatment by a corrosion treatment with an iron (III) chloride solution or ammonium perchlorate. The radiation-cured coating is subsequently removed on the circuit pattern by treatment with a solvent which is stronger than that used in the development, in which case a printed circuit is produced on the substrate. . However, solvents similar to those used for development may be used only under sharp conditions.

For this so-called stripping process, concentrated caustic soda liquor or potassium hydroxide liquor can be used, for example, in the case of a resin having an acid group, and in the case of a resin having a basic group, a concentrated acid, for example, Sulfuric acid can be used.

Another method for producing the conductor plate consists in depositing another copper by electroplating until a layer thickness of the copper film of 30-35 μm is reached after development on the exposed copper surface. At this point in the strengthened copper layer there is a later conductive path. The film polymerized as described above is then removed under sharp conditions by treatment with a more concentrated solvent or with a solvent similar to that used for development. In addition, the exposed metal is corroded, as described above. This method must apply only a significantly thin copper layer of 0.5-5 μm per difference, which thin copper layer serves exclusively to coat the substrate with a conductive layer, and thereby electrophoretically. And has the advantage that it can be coated with a resist material. Furthermore, in the case of this method, it is necessary to corrode a very small amount of copper (so-called differential corrosion), which is another important advantage.

Now, the present invention will be described in detail with reference to Examples. In this case, all references to percentages and parts are by weight, unless stated otherwise.

1. Preparation of Polymer Component A Polymer A was prepared in a reactor equipped with a nitrogen feed tube, stirrer and metering device. The composition of the monomers of the polymer is given in Table 1.

All polymers are prepared in xylol with 50% polymerized solids at a polymerization temperature of 110 ° C. under a nitrogen supply. Azoisovaleronitrile is used as an initiator in an amount of 4%, based on the weight of the monomers. As a regulator, mercaptoethanol is used in an amount of 1% with respect to the weight of the monomers, respectively. In this case, the modifier is fed with the monomer in 4 hours. The initiator is fed in the form of a 10% solution in xylol via a separate feeding tube in 4.5 hours. Subsequently, the temperature is maintained at 110 ° C. until 50% of the theoretical solid (20 min, 180 ° C.) is reached (about 3-4 hours).

Subsequently, by modifying the obtained polymer with glycidyl methacrylate as component a ₆ , in an air atmosphere.
Chromium octenoate 0.1% as catalyst at temperature of 90 ℃, 2,6
-Di-tert-butyl-p-cresol 0.1% and phenothiazine 0.05% as a polymerization inhibitor,
All percentages given here are by weight of the monomers used, including glycidyl methacrylate. In this case, the reaction is allowed to proceed until the theoretical acid number is reached. The xylol is subsequently distilled off until a solids content of 70% is reached (1 hour, 130 ° C.).

Example 1 A 70% solution of polymer A1 is partially neutralized with dimethylethanolamine. The degree of neutralization (NG) is listed in Table 1. After that, the remaining components of the coating (monomer B, photoinitiator C) are added and subsequently transferred into the dispersion with stirring by the gradual addition of distilled water. The composition of the resulting aqueous coating 1 is given in Table 2.

Subsequently, the aqueous coating material 1 was continuously stirred in the dark.
Stirring was carried out at 30 ° C. for 7 days to evaporate the readily volatile solvent content, eg xylol, after which precipitation and testing were carried out.

The deposition of the lacquer film is carried out in a 3 l container at a bath temperature of 25 ° C.
Performed using 2.5l. For this purpose, a cleaned and degreased copper laminate (immersion area 230 cm ² ) is connected as an anode and coated.

A special steel sheet (immersion area 70 cm ² ) immersed in a bath liquid is used as the counter electrode. In this case, the precipitation condition is about 3
It is selected to give a lacquer coating with a dry coating layer thickness of 0 μm. The required precipitation data are likewise given in table 2. The coated laminate is subsequently dried at 80 ° C. for 20 minutes in a circulating air oven. 24 at room temperature
After storage for a period of time, the lacquer coating is partially covered with a commercial mask and then cured by irradiation with a medium pressure mercury lamp (lamp power 80 W / cm). In this case, the distance between the lamp and the coated substrate is 25 cm. The lamp is arranged perpendicular to the transport direction. The feeding speed of the conveyor belt is adjusted to a value between 1 and 20 m / min. The maximum feed rates which ensure that the cured coating shows no surface changes in the developing bath are listed in Table 3.

The coatings obtained were subsequently subjected to the following tests: 1. Developability: After exposure, the unexposed parts of the lacquer coating are removed by dipping the coated copper laminate in a 2% sodium carbonate solution. In this case, the sodium carbonate solution has a temperature of 20 ° C. and is stirred at 200 rpm.

2. Stability to copper plating bath: To test the stability of the lacquer coating to the copper plating bath, the exposed copper laminate is allowed to stand at room temperature for 1 hour at 20% sulfuric acid.
And an aqueous solution containing 2% of copper sulfate. The surface of the lacquer coating is subsequently evaluated (iO = no change in lacquer surface). The test results are listed in Table 3.

3. Peelability: The hardened part of the lacquer coating is removed by dipping the developed copper laminate in a 3% sodium hydroxide solution. In this case, the sodium hydroxide solution has a temperature of 20 ° C. and is stirred at 200 rpm. The immersion time required to strip the exposed areas is listed in Table 3.

Example 2 An aqueous coating 2 is prepared in the same manner as in Example 1, this aqueous coating 2 being distinguished from the aqueous coating 1 only by using a solution of the polymer A2 instead of a solution of the polymer A1. It The composition of this coating material 2 is given in Table 2.
Deposition of this aqueous coating 2 and curing and testing of the resulting coating are carried out as in Example 1. The result is the second
See Tables and Table 3.

Comparative Examples 1 to 4 Various aqueous coating agents V1 to V4 were prepared in the same manner as in Example 1, in which these aqueous coating agents used solutions of polymers V1 to V4 instead of solutions of polymer A1. Is distinguished from the aqueous coating agent 1 only. The composition of the coating materials V1 to V4 is the second
Listed in the table.

The deposition of the aqueous coatings V1 to V4 and the curing and testing of the resulting coating are carried out as in Example 1. The results are listed in Tables 2 and 3.

Example 3 Aqueous coating 3 is prepared in the same manner as in Example 2, where 3% of trimethylolpropane triacrylate is used instead of 3% of trimethylolpropane triacrylate based on the total weight of the aqueous coating. It is distinguished from aqueous coating 2 only by using%.

Deposition of this aqueous coating 3 and curing and testing of the resulting coating is carried out as in Example 2. Precipitation data and test results are listed in Table 4.

Comparative Examples V5 to V7 Aqueous coatings V5 to V7 are prepared in a manner similar to Comparative Examples 2 to 4, these aqueous coatings V5 to V7 being each trimethylolpropane triacrylate based on the total weight of the aqueous coating. Aqueous coating V2 only by using 5% trimethylolpropane triacrylate instead of 3%
~ Differentiated from V4.

The deposition of this aqueous coating V5 to V7 and the curing and testing of the resulting coating are carried out as in Example 1. Precipitation data and test results are listed in Table 4.

Summary of Test Results for Examples 1-3 and Comparative Examples V1-V7 Comparative Example V2 shows that introduction of hexanediol dimethacrylate into the polymer can increase the stripping voltage. However, it is disadvantageous that the introduction of hexanediol dimethacrylate significantly increases the curing time, which reduces the achievable transport speed from 10 m / min to 1 m / min. Therefore, curing of this system is not possible under economically advantageous conditions. Moreover, despite the high acid number of the coating, it is disadvantageous that the stripping time with a 3% sodium hydroxide solution cannot be reduced to an economical time.

The coating material of Comparative Example 1 actually exhibits a peeling voltage of 300V,
Therefore, sufficient hugging or winding behavior can be achieved with this coating. However, the remaining properties of the coating are quite unsatisfactory for use as a photoresist material. That is, despite the relatively low double bond equivalent and thus the high double bond density, only a feed rate of 1 m / min can be adjusted in order to achieve a sufficient cure. Furthermore, despite the high acid value of the coating agent, 3
% Peeling time with 10% sodium hydroxide solution
It is disadvantageous to reduce the economic time below.

The coatings of Comparative Examples 3, 4, 6 and 7 show peel voltages which are significantly too low for practical use.

In contrast to this, the coatings of Examples 1 and 2 simultaneously produced 450 times good curing times, developability and peelability.
Or it shows a high peeling voltage of 400V.

Comparison of Examples 2 and 3 with Comparative Examples V2-V4 and V5-V7 shows the effect of monomer component B. The advantage of the increased stripping voltage with the coating according to the invention is that of Example 3 and Comparative Examples V5 to V7.
Especially when the amount of component B is higher than when the comparison with.

Example 4 A glass fiber reinforced epoxy resin laminate, commonly used in the production of conductor plates, with a copper layer 3-5 μm thick is electrophoretically coated with an aqueous coating 2. Deposition conditions are as follows: Deposition voltage 325V Deposition time 120s Bath temperature 25 ° C Anode / cathode distance 10cm Area ratio of laminated product to cathode 2: 1 Dry coating layer thickness 25μm Complete removal of adhering bath material Washed with brine. The coated laminate is subsequently dried at 80 ° C. for 10 minutes in a circulating air oven. After being covered with a commercial photomask, the coating is cured by irradiation with a medium pressure mercury lamp (irradiation power 100 J / cm ² , measured on lacquer surface). The unexposed parts of the lacquer coating are subsequently stripped by treatment with a 3% sodium hydrogen carbonate solution in a suitable spray chamber. In this case, the side surface of the remaining material is smooth and steep. Subsequently, the exposed copper surface is 30 μm in a commercial electroplating bath.
Of the lacquer layer without damaging the lacquer layer. In addition, the exposed parts of the lacquer coating are removed by treatment with a 3% sodium hydroxide solution in a suitable spray chamber for 5 minutes. Afterwards, the electroplating-enhanced conductive paths are obtained by differential corrosion using a commercial corrosion solution based on sulfuric acid.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Volkmann, Bernd-Rüdiger, Federal Republic of Germany D-4400 Munster Bachstraße 21 (72) Inventor Hoppe-Hehler, Monica United States Michigan 48322 W. Bloomfield Olding Brook Heritage 6461 (56) Reference JP 61-80240 (JP, A) JP 62-262855 (JP, A) JP 62-262856 (JP, A) JP 1-122189 (JP, A) JP-A-2-20873 (JP, A) JP-A-2-213485 (JP, A) JP-A-4-66948 (JP, A) JP-A-4-116181 (JP, A)

Claims (3)

[Claims] 1. A) 35 to 85% by weight of at least one ethylenically unsaturated, water-dispersible or water-soluble polymer, B) 0 to 60% by weight of at least one ethylenically unsaturated monomer, C) at least One photoinitiator 1 to 10% by weight, D) auxiliaries and additives 0 to 10% by weight and E) optionally containing an organic solvent dispersed in water, provided that the weight proportions of components A to D are The sum of each is 10
0% by weight), in a water-developable, electrodepositable and photocurable negative type coating, the polymer A is 1500 to 10
Having a double bond equivalent of 000 and an anion or cation forming group content of 0.5 to 5.0 milliequivalents, and I. In the first step, a ₁ ) at least 2 ethylenically unsaturated polymerisable per molecule double bonds and a number average molecular weight <400, at least one monomer from 5 to 30 wt% having a, a ₂₎ at least one having at least one anion or cation forming group and / or at least one functional group Ethylenically unsaturated copolymerizable monomer 5-30
%, A ₃ ) 40-80% by weight of at least one other ethylenically unsaturated copolymerizable monomer without anion or cation-forming groups, excluding vinyl aromatic hydrocarbons, a ₄ ) 0 to 50% by weight of at least one vinyl aromatic hydrocarbon (provided that the total weight content of the components a _{1 to} a ₄ is 100 in each case).
%.) By radical copolymerization II. The functional groups of the resulting copolymer are a ₅ ) at least one anion or cation-forming group and the groups and numbers capable of reacting with the functional groups of the copolymer. At least partially reacted with at least one compound having an average molecular weight <300 of 2 to 85% by weight (based on the total weight of components a _{1 to} a ₄ ), III. This copolymer a ₆ ) of at least one At least one compound having a group capable of reacting with an ethylenically unsaturated double bond and an anion or cation forming group of component a ₂ or a ₅ and / or a functional group of the copolymer, and a number average molecular weight <300 2 ~ 2
0% by weight (based on the total weight of components a _{1 to} a ₄ ),
And IV. A water-developable, electrodepositable and photocurable negative mold, characterized in that it is prepared by at least partially neutralizing the anion- or cation-forming groups of the resulting copolymer. Coating agent. 2. A) an aqueous coating is electrophoretically deposited on a copper surface; 2.) A portion of the deposited coating is irradiated with an actinic radiation source; On the surface, develop the unexposed part of the coating by dissolving it in an aqueous solution, 4.) remove the exposed copper surface by a corrosive bath or deposit more copper by electroplating on the exposed copper surface. And 5.) removing the exposed surface of the polymer coating with an aqueous solution, and 6.) depositing copper by electroplating in the fourth treatment step, the copper exposed in the fifth treatment step. A method of manufacturing a printed circuit by removing the surface by differential corrosion, comprising electrophoretically depositing the coating according to claim 1 on a copper surface in a first step. Manufacturing method. 3. A method for producing a two-dimensional, 2 1 / 2-dimensional and three-dimensional conductor plate, characterized in that the coating material according to claim 1 is used. / A method for manufacturing two-dimensional and three-dimensional conductor plates.