WO1993011465A1 - Composition photopolymerisable contenant des reticulats polymeriques epoxy et allyliques lies les uns aux autres - Google Patents

Composition photopolymerisable contenant des reticulats polymeriques epoxy et allyliques lies les uns aux autres Download PDF

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Publication number
WO1993011465A1
WO1993011465A1 PCT/EP1992/002332 EP9202332W WO9311465A1 WO 1993011465 A1 WO1993011465 A1 WO 1993011465A1 EP 9202332 W EP9202332 W EP 9202332W WO 9311465 A1 WO9311465 A1 WO 9311465A1
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WIPO (PCT)
Prior art keywords
photopolymerizable composition
composition according
allylic
photopolymerizable
epoxy
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PCT/EP1992/002332
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English (en)
Inventor
Ricardo Henry Breeveld
Jan André Jozef SCHUTYSER
Original Assignee
Akzo Nobel N.V.
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Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Publication of WO1993011465A1 publication Critical patent/WO1993011465A1/fr

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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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks

Definitions

  • the invention pertains to a photopolymerizable composition
  • a photopolymerizable composition comprising a mixture of interpenetrating network-forming monomers and a photo- initiator, the interpenetrating network-forming monomers comprising
  • Photopolymerizable, or photosensitive compositions also referred to as “photoresists" are compositions which upon irradiation undergo a change in physical properties, notably involving solubility or extractability in a developer liquid.
  • photoresists are compositions which upon irradiation undergo a change in physical properties, notably involving solubility or extractability in a developer liquid.
  • the initial composition is solvent-extractable and becomes solvent-resistant upon irradiation.
  • Photoresists can be used to define patterns made up of covered and uncovered portions of a substrate. They are widely used, e.g. in manufacturing printed wiring boards (PWBs), either as an imaging resist at the stage where a conductive pattern is defined, or as a solder mask to protect selected areas of the conductive pattern from the action of molten solder.
  • PWBs printed wiring boards
  • the present invention particularly pertains to photopolymerizable compositions that can be used as imaging resists in additive plating processes involving hot alkaline plating baths.
  • a permanent resist is applied to a substrate and irradiated through a master image, in order to define the pattern where metallization should take place.
  • the developed photosensitive composition should be resistant to the hot alkaline medium.
  • photoresists may be referred to as permanent additive resists.
  • the present invention also pertains to photopolymerizable compositions that can be adapted for use as a platable surface.
  • Platable resists are used in processes for the manufacture of multilayer printed circuit boards in which, usually, additive plating techniques are employed. Such processes (“sequential multilayer processes") have been described in WO 91/6423 and US 4,737,446, both of which are incorporated by reference for all purposes.
  • a basic requirement for electroless pl tability is that conventional additive catalysts can be added to the bulk and/or onto the pre-treated surface of the resist. The main requirement is that, once such catalysts are present, the 'photoresist can be plated so as to achieve favourable metallization with sufficient bond strength.
  • a photopolymerizable composition of the type mentioned in the opening paragraph is known from Japanese Patent Application Laid-Open No. 62/265-321.
  • the compound having at least two allylic functional groups is a prepolymer of diallyl phthalate.
  • the cross!inker reactive towards epoxy is a mixture of a diamino triazine-modified imidazole compound and dicyanodiamide.
  • One object of the present invention is to provide a photocurable composition without a dicyanodiamide epoxy crosslinker in which the resist's properties are not adversely affected, e.g. no spelling.
  • free amino groups are present in the disclosed compositions, which is known to have a negative impact on the storage-stability of epoxy-containing compositions. In particular this is a drawback in the case of one-pot systems, which in commercial practice are preferred.
  • the photopolymerizable compositions of the instant invention it is very well possible, and indeed preferred, to avoid the use of amino and/or cyano groups-containing epoxy curing agents.
  • the invention has for one of its objects to provide a photopolymerizable composition which allows of a relatively wide choice of ingredients but is sufficiently resistant still towards increased temperatures, organic solvents, and hot alkali. Another object of the invention is to further improve these properties as compared with the known photoresist.
  • photopolymerizable compositions having some resistance towards hot alkali are known. Such permanent additive resists have been described, e.g., in EP-A-270 945.
  • the disclosed photopolymerizable composition comprises a monomeric component comprising a half-acryloyl ester of bisphenol-A epoxy monomer, an initiating system activated by actinic radiation, and an elastomeric polymeric binder.
  • the EP-A-270 945 compositions are said to withstand contact for 24 hours with a liquid at pH 12 maintained at a temperature of 70°C, the alkali resistance should be improved for the compositions to function favourably in a commercial additive plating process.
  • a further drawback is the presence of an elastomeric binder. These rubber-type components tend to lead to a high oxygen sensitivity, which has a negative effect on the product's performance and properties.
  • a permanent additive resist which in practice displays more acceptable results is the PAR1 Riston ® dry film photoresist ex DuPont de Nemours and Company. Though the alkali resistance is satisfactory, there is still room for further improvement. Besides, the above-mentioned drawback of oxygen sensitivity applies.
  • a serious further drawback to the aforementioned permanent additive resists is the occurrence of extraneous growth of the conductive metal when the photo-imaged substrate is immersed in the additive plating bath, and the leaching of organic constituents of the composition into the plating bath. These drawbacks may lead to metallization beyond the desired pattern and contamination of the plating bath, resulting in a less favourable yield in PWB production. Said problems of extraneous metal-growth and bath contamination associated with PAR1 are not incurred with the composition according to the present invention.
  • IPN interpenetrating polymer network
  • EP-A-359 216 a photopolymerizable composition which upon curing forms an interpenetrating polymer network
  • IPNs comprising an epoxy resin network produced from an acidified epoxy resin and a network of a polymer produced by the polymerization under the influence of radicals of a monomer which at room temperature is solid or has a viscosity greater than 1 kPa.s.
  • di- and triacrylates are di- and triacrylates.
  • the networks which make up the IPN are not interlinked.
  • the acidified epoxy oligomer prescribed in EP-A-359216 preferably is avoided in the composition of the present invention. A drawback to said oligomer is its low stability upon storage.
  • EP-A-359216 composition is enhanced by means of corrosive, hence disadvantageous Lewis acids.
  • the concept of a polymeric material comprising chemically linked allylic and epoxy polymer networks is known from EP-A-417837. The disclosure does not pertain to photopolymerizable compositions.
  • a photosensitive resin which comprises a half ester of a hydroxyalkyl (meth)acrylate and a styrene-maleic anhydride copolymer, a multifunctional (meth)acrylate monomer, a multifunctional epoxide, and a photo-initiator.
  • the epoxide serves to provide more stable crosslinking of the photopoly er.
  • JP 57/16446 the use of triallyl trimellitate as a photosensitive compound is disclosed.
  • the disclosure does not pertain to IPNs.
  • Still another object of the present invention is to provide a generally favourable photosensitive composition which is especially viable as a permanent additive resist or a platable resist, and has a particularly good resistance towards hot alkali .
  • the invention consists of a photopolymerizable composition of the above known type which comprises at least one compound having both an ethylenically unsaturated functional group and a functional group reactive towards at least one of the ingredients in the mixture capable of forming an epoxy resin network.
  • the invention thus pertains to a photocurable mixture in which at least one ingredient serves as a means for interlinking the unsaturated double bond based polymer network and the epoxy resin network.
  • a curable mixture generally comprises monome.ric, oligomeric, or prepolymeric compounds which, upon polymerization, form a three-dimensional polymer network.
  • two such networks viz. the unsaturated double bond based polymer network and the epoxy resin network, are produced by different chemical mechanisms. This results in the formation of an interpenetrating network (IPN).
  • IPN interpenetrating network
  • the networks producing the IPN are linked to each other.
  • the unsaturated double bond based polymer network will be referred to hereinafter as allylic polymer network.
  • a multifunctional compound containing both allylic and epoxy moieties instead of, or in addition to, the allylic compound contained in monomer mixture (a).
  • Such a compound may also be used instead of, or in addition to, the epoxide contained in monomer mixture (b) .
  • Such a multifunctional compound is capable of reacting according to both network-forming mechanisms, resulting in the two networks being linked to each other. Al ernatively, the networks are interlinked by means of the epoxy crosslinker.
  • a cross!inker which has one or more functional groups reactive towards epoxy, and which further comprises an unsaturated chemical bond copolymerizable with the monomers contained in network- forming mixture (a).
  • an epoxy compound containing a polymerizable unsaturated chemical bond may be employed.
  • the photopolymerizable composition of the present invention forms a polymeric material comprising chemically linked allylic and epoxy polymer networks.
  • interl nked IPNs does not teach the man skilled in the art to employ a chemically linked interpenetrating polymer network of the disclosed type in a photopolymerizable composition, nor does it lead him to expect any of the advantages obtained with the photopolymerizable composition of the instant invention.
  • photo-initiation leads to different reaction kinetics than thermal initiation. It is believed, though such theory should not be considered to be binding, that in the thermally cured interlinked IPN of EP 417 837 the two networks are formed simultaneously.
  • the polymer network formed by photo-initiated polymerization of the ethylenically unsaturated compounds (a) is believed to be formed first.
  • the epoxy resin network is formed by means of the (thermally initiated) crosslinking reaction of mixture (b).
  • the photopolymerizable composition according to the present invention displays further advantages, both of general value to photoresists and of specific value to permanent plating resists.
  • allylic and epoxy networks can be provided.
  • multifunctional molecules containing allylic and epoxy moieties include those described in J. Appl. Polym. Sci. 36(7), DE-OS-3037 094, and Japanese Patent Applications Laid-Open Nos. 61/120746, 60/081225, 55/021455, 55/072304.
  • Suitable multifunctional molecules can generally be prepared by epoxidation of part of the ally! groups in polyallyl compounds. Such epoxidation has been described in CA. May's Epoxy Resins (to be referred to later).
  • crosslinkers which are reactive towards epoxy and copolymerizable with allyl include cyclic carboxylic anhydrides containing a polymerizable unsaturated carbon-carbon bond, e.g., maleic anhydride, itaconic anhydride, citraconic anhydride, half-esters of the corresponding dicarboxylic acids and of isomeric d carboxylic acids, such as fumaric acid.
  • the esterifying alcohol or alcohols are not particularly critical, but lower alcohols, such as methanol, ethanol, propanol, iso-propanol, butanol, pentanol, hexanol, and the like, are preferred.
  • half-esters of dicarboxylic acids in which the esterifying alcohol contains a polymerizable unsaturated carbon-carbon bond, such as allylic alcohol, hydroxy methyl acrylate, hydroxy methyl methacrylate, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, as well as other hydroxy(alkyl) (meth)aerylates, and the like.
  • suitable crosslinkers include carboxyl terminated oligo(ester) reaction products of dicarboxylic acids having a polymerizable double bond, such as maleic acid, and aliphatic or aromatic dio s.
  • Such a crosslinker having a polymerizable unsaturated carbon-carbon bond is the preferred means of interlinking the allylic and the epoxy polymer networks.
  • this crosslinker is an anhydride or a half-ester of an ⁇ , ⁇ -unsaturated dicarboxylic acid, or a mixture thereof.
  • maleic anhydride An additional advantage of maleic anhydride is that it enhances the polymerization rate of the allylic monomers.
  • the crosslinker does not need to contain a polymerizable unsaturated carbon-carbon bond.
  • Suitable crosslinkers that may be used in this respect include saturated carboxylic anhydrides, such as hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, Nadic® methyl anhydride, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, trimellitic anhydride.
  • accelerators for the thermal reaction of the epoxide and the crosslinker are, e.g., imidazoles, notably alkyl substituted imidazoles such as 2-methyl imidazole and 2-ethyl 4-methyl imidazole.
  • Examples of compounds having at least two allylic functional groups include cyanuric compounds, such as triallyl cyanurate (TAC) monomer or trially! isocyanurate (TAIC) monomer, TAC or TAIC oligomers or prepolymers; aromatic polyallyl esters, such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, diallyl tetrabromophthalate; aliphatic polyallyl esters such as diallyl adipate, diallyl maleate, diallyl fumarate; polyallyl carbonates such as diethylene glycol diallyl carbonate, and the like. It is very well possible to use mixtures of allyl compounds. It is preferred to use TAC or TAIC monomers, oligo ers or prepolymers, or multifunctional allyl compounds in which the allylic moieties are TAC or TAIC moieties.
  • TAC triallyl cyanurate
  • difunctional epoxide is used to indicate the compounds present in a curable composition of oxirane ring-containing compounds. Such a curable composition may also be referred to simply as "epoxy resin”. Said compounds have been described in CA. May's Epoxy Resins, 2nd Edition, Marcel Dekker Inc., New York & Basle, 1988. Further reference can be made to the aforementioned EP 417 837, which is hereby incorporated by reference for all purposes.
  • Preferred epoxy resins are phenol types, such as those based on the diglycidyl ether of Bisphenol-A, on polyglycidyl ethers of phenol- formaldehyde Novolac or cresol-formaldehyde Novolac, on the triglycidyl ether of tris(p-hydroxyphenol)methane, or on the tetraglycidyl ether of tetraphenyl ethane; amine types, such as those -based on tetraglycidyl methylene diam " line or the triglycidyl ether of p-aminoglycol; cycloaliphatic types, such as those based on 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.
  • the epoxide may also be a multifunctional compound containing both allylic and epoxy moieties. Multifunctional compounds having epoxy and vinylic moieties copolymerizable with allylic compounds are suitable as well.
  • the ethylenically unsaturated compounds (a) may be exclusively allylic compounds (al).
  • the photochemical curing speed may be improved by incorporating into the photopolymerizable composition according to the present invention monomers present in conventional photoresists, i.e. photopolymerizable vinylic monomers (a2). Due to the presence of these monomers faster curing speeds and hence the economically most feasible manufacturing processes are realized.
  • Suitable photopolymerizable vinyl ic monomers include monomers polymerizable under the influence of radicals-generating photo-initiators and monomers polymerizable under the influence of cationic photo-initiators.
  • vinyl ic monomers polymerizable under the influence of photo-generated radicals are monomers, such as styrene, diisopropenyl benzene, triisopropenyl benzene.
  • Other examples include acrylic and methacrylic monomers, such as t-butyl
  • (meth) acrylate ethylene glycol di (meth)acrylate, butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexa ethylene glycol di (meth) acrylate, prooanediol di ( eth)acrylate, decamethylene glycol di (meth) acrylate, cyclohexanediol di (meth) acrylate, dimethyl ol propane di (meth) acrylate, glycerol di (meth)acrylate, tripropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetraacrylate, tri s (2-hydroxyethyl ) i socyanurate tetraacryl ate .
  • Examples of monomers polymerizable under the influence of cationic photo-initiators include vinyl ethers, e.g. alkyl vinyl ethers such as ethyl vinyl ether, isopropenyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether; substituted alkyl vinyl ethers, such as chloroethyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, methoxyphenyl vinyl ether, tolyl vinyl ether; substituted aryl vinyl ethers, such as chlorophenyl vinyl ether.
  • alkyl vinyl ethers such as ethyl vinyl ether, isopropenyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether
  • substituted alkyl vinyl ethers such as chloroethyl vinyl ether
  • aryl vinyl ethers such as phenyl vinyl ether, methoxypheny
  • Preferred photopolymerizable vinylic monomers are trimethylol propane triacrylate and trimethylol propane tri ethacrylate.
  • Photo-initiators are known in the art, and can be generally described as compounds producing highly reactive species, such as free radicals, upon actinic radiation, e.g. UV radiation.
  • radicals-generating photo-initi tors include well-known vicinal ketaldonyl alcohols, such as benzoin, pivaloin, acyloin ethers, e.g. benzoin methyl and ethyl ethers; -hydrocarbon substituted aromatic acyloins such as ⁇ -methyl benzoin, ⁇ -allyl benzoin, ⁇ -phenyl benzoin; phenazine, oxazines, quinones; Michler's ketone (tetramethyl diamino benzophenone), benzophenone; substituted or unsubstituted polynuclear quinones, e.g.
  • anthraquinone chloroanthraquinone, methyl nthraquinone, ethylanthraquinone, t-butyl anthraquinone, octamethyl anthraquinone, naphthoquinone, phenanthrenequ none, benzanthraquinone, methyl naphthoquinone, dichloronaphthoquinone, dimethylanthraquinone, phenylanthraquinone, diphenylanthraquinone, and the like. Combinations of two or more photo-initiators are frequently applied. In this respect a mixture of benzophenone and a minor amount of Michler's ketone is found to be advantageous.
  • Suitable photo-initiators include those initiating cationic polymerization reactions, such as the polymerization of vinyl ethers, and those liberating free acids and thus initiating acid-hardening reactions, such as epoxy polymerization.
  • Such cationic photo- initiators are, e.g., arylsulpho ⁇ iurn and aryliodonium salts.
  • suitable cationic photo-initiators are known from, e.g., EP 166682, EP 84515, EP 89922. It should be noted that, as the artisan knows, photo-initiators frequently are present in the form of a photo-initiating system.
  • a sensitizer i.e. a compound which is capable of absorbing radiation energy and transferring said energy to the actual photo-initiator.
  • Photoreducible dyes may also be present. Examples of photo-initiating systems include those described in EP-A-270945, which is hereby incorporated by reference for all purposes.
  • photo-initiating systems sensitive to 488 nm may be used. These systems are advantageous in the case of so-called “direct imaging", where an Ar + ion laser is employed to create the desired image without a mask being used.
  • a further possible constituent of the photopolymerizable compositions of the present invention is a film-forming polymeric binder.
  • a binder may be an elastomer, these are not to be preferred, as indicated above. It is an advantage of the current invention that even without a rubber component the photoresists obtained still display the required elasticity.
  • non-rubber film-forming binders include polyacrylate and ⁇ -alkyl polyacrylate esters, e.g.
  • polymethyl methacrylate and polyethyl methacrylate polyvinyl esters such as polyvinyl acetate, and copolymers thereof with polyvinyl (meth)acrylate, hydrolyzed polyvinyl acetate, ethylene/vinyl acetate copolymers, polystyrene, and copolymers of polystyrene with, e.g., maleic anhydride and esters, copolymers of vinylidene chloride and, e.g., acrylonitrile, methacrylate, vinyl acetate, polyvinyl chloride, and copolymers, e.g. with polyvinyl acetate.
  • Unsaturated polyesters are also suitable binders, i.e., the condensation products obtained by polycondensation of unsaturated dicarboxylic acids or anhydrides, such as maleic anhydride, citraconic anhydride, fumaric acid, with polyhydric alcohols such as ethylene glycol or 1,2-propylene glycol.
  • binders i.e., the condensation products obtained by polycondensation of unsaturated dicarboxylic acids or anhydrides, such as maleic anhydride, citraconic anhydride, fumaric acid, with polyhydric alcohols such as ethylene glycol or 1,2-propylene glycol.
  • the aforementioned ingredients may be present in a wide range of ratios.
  • the allylic compounds (al) and the epoxy resin network forming mixture (b) are present in a weight ratio of (al):(b) in the range of from 70:30 to 30:70, more preferably of from 60:40 to 40:60.
  • the crosslinker will generally be present in a molar ratio of about 0.5 to 1.5 functional groups reactive towards epoxy per epoxy functional group.
  • a preferred range is of from about 0.8 to about 1.2.
  • the molar ratio of allylic functional groups to epoxy functional groups preferably is in the range of from about 6 to about 1.
  • the crosslinker most preferably is present in an amount about equimolar to the epoxy functional groups.
  • the photo-initiator generally is present in an amount of 0.5 to 20 wt%, preferably 2-10 wt%, of the total composition. If present, the photopolymerizable monomers may make up any amount up to about 80% of the entire composition. The same holds for the film-forming binder.
  • the instant invention pertains to a photopolymerizable composition
  • a photopolymerizable composition comprising about 29-74 wt% of the curable mixture of ingredients (al) and (b) described hereinbefore, about 3-6 wt% of the photo-initiator, about 15-46 wt% of the photopolymerizable monomers (a2), and up to 40 wt% of the film-forming binder.
  • the photosensitive compositions of the present invention may further contain additives such as those commonly present in photoresists. These include dyes, pigments, inhibitors, wetting agents, release agents, fillers. Examples include talc, aluminium silicate pigments, alumina tetrahydrate, alumina spheres, barium sulphate pigment, fumed silica and amorphous silica. These and other additives are known in the art, and need not be discussed here to explain the instant invention.
  • the invention provides a platable resist.
  • Platable resists can be employed to define a pattern that should be metallized, the metallization in this case occurring on the surface of the resist.
  • Platable resists thus can be used to build a multilayer printed wire board with conductive vias rather than plated through holes.
  • a photoresist should be rendered catalytic for additive (electroless) plating.
  • the mere addition of catalyst to just any photoresist does not generally render such a photoresist suitable for additive plating.
  • the resist withstand the plating conditions mentioned earlier.
  • the resist's mechanical, thermal, and electrical properties must also be sufficient to serve as a substrate for conductive circuitry.
  • the photopolymerizable compositions of the invention satisfy these requirements, and can be rendered suitable for additive plating by the mere addition of a catalyst.
  • Suitable catalysts include noble metals and noble metal compounds, palladium being preferred. More specifically: as a catalyst to be added to the bulk of the photoresist palladium and/or palladium chloride are preferred, dispersed or not in an inorganic or organic matrix (e.g. Pd in clay).
  • an inorganic or organic matrix e.g. Pd in clay.
  • 9F seeding is preferred, as well as the methods described in EP 430333 and US 4,701,351.
  • Solvents may also be present in the photopolymerizable compositions of the present invention.
  • Suitable solvents include dimethyl formamide; glycol ethers, such as ethylene glycol onoethyl ether or propylene glycol monoethyl ether, and esters thereof, such as ethylene glycol monoethyl ether . acetate; ketones, such as methyl isobutyl ketone, methyl ethyl ketone (MEK), acetone, methyl isopropyl ketone; lactones such as gamma-butyrolactone; aromatic hydrocarbons, such as toluene and xylene, N-methyl pyrrolidone (NMP).
  • NMP N-methyl pyrrolidone
  • the preferred solvents are ketones, notably MEK, and NMP, by further preference in admixture with isopropyl alcohol (IPA); and Dowanol®PMA (propyleen glycol methylether acetate).
  • IPA isopropyl alcohol
  • Dowanol®PMA propyleen glycol methylether acetate
  • a further advantage of the instant photopolymerizable compositions is that the use of solvents may be omitted, notably if TAC is used as the allylic monomer.
  • Another disadvantage of the composition disclosed in JP-A-62/265-321 viz. the necessity to use a relatively large amount of solvent in order to provide the diallyl phthalate prepolymer-based photopolymerizable composition with the desired processability, can be overcome.
  • compositions of the present invention may be used either in the form of a liquid resist, which is applied, e.g., by spraying onto a substrate, or in the form of a so-called dry film resist, which is usually applied to a substrate by roll lamination.
  • the compositions of the present invention are particularly useful in curtain coating processes.
  • a substrate is passed through, and is perpendicular to, a freely falling liquid resist curtain and so coated with the photopolymerizable composition.
  • the liquid resist generally has a viscosity of about 150 to 20000 Pa. With the compositions of the present invention viscosities in the desired range can easily be obtained, notably by varying the solid content.
  • a sandwich in which the photopolymerizable composition is present between a support layer, e.g. a polymeric layer such as polyethylene, and a.protective layer (e.g., polyethylene terephthalate foil).
  • a support layer e.g. a polymeric layer such as polyethylene
  • a.protective layer e.g., polyethylene terephthalate foil
  • the instant invention also pertains to a dry film resist comprising a photopolymerizable composition as described hereinbefore.
  • the photo-imaging process itself is known in the art and involves irradiating the photoresist-covered substrate through a master image, resulting in certain portions being polymerized and other portions remaining uncured.
  • the resist of the instant invention is also suitable for screen-printing.
  • the photocurable composition is applied to a substrate by being passed through a screen which defines the desired image.
  • the photocuring treatment is carried out until the polymerized parts are sufficiently resistant towards the developer liquid used for the subsequent removal of the portions not subjected to irradiation.
  • the irradiation generally is UV irradiation.
  • a preferred light source used is a high pressure mercury arc.
  • a typical irradiation process as used in commercially operating PWB plants will involve an initial exposure of several seconds and a holdtime of a few minutes, followed by development. After the developing process the remaining portions of the photoresist are subjected to heat treatment in order to obtain complete curing.
  • Suitable developers include the solvents in which the photopolymerizable composition of the present invention may be dissolved. Of course it is of importance that the irradiated, though not completely cured portions of the photosensitive composition be resistant towards the developer.
  • Suitable developers include acetone, 1,1,1-trichloroethane, heptane, Dowanol PMA, IPA/heptane mixture, y-butyro lactone, methyl isobutyl ketone, xylene.
  • halogenated hydrocarbons such as trichloroethane are not to be preferred.
  • a further advantage of the present invention to be mentioned is that the instant photopolymerizable compositions display a significantly higher initial • 5 solvent resistance towards less hazardous developers, such as heptane, IPA, Dowanol PMA, than state of the art additive plating resists do.
  • the invention a so pertains to a method of using a photopolymerizable composition according to any one of the embodiments described hereinbefore to provide a substrate with a photodefined layer, the 0 method comprising the steps of (i) applying the photopolymerizable composition to a substrate, resulting in the substrate being coated with a photosensitive layer, (ii) exposing selected portions of the photosensitive layer to
  • UV-light of sufficient energy to result in the exposed portions being initially cured, while the non-exposed portions remain uncured, (iii) contacting the partially irradiated layer with a developer liquid to remove the uncured portions of the photosensitive layer, thus leaving a photodefined coating on the substrate, (iv) subjecting the photodefined coating to thermal treatment in order to increase the degree of curing, (v) exposing the photodefined coating to UV-light, optionally in conjunction with heat, in order to effect further curing, to give a photodefined laminate comprised of the substrate coated with a permanent photodefined layer.
  • the substrate may be a base material for the additive manufacture of printed wiring boards.
  • the permanent photodefined layer in such a case is used as a permanent plating resist mask.
  • the mask is resistant towards hot alkali and does not lead to extraneous copper growth, nor does it cause contamination of the plating bath with leachables, thus leading to a higher yield of printed wiring boards and causing the manufacture thereof to be a more economically advantageous operation.
  • the manufacture of printed wiring boards by additive metallization of a substrate susceptible to additive plating is known in the art, and need not be explained in detail here. Instead, reference is made to Clyde F. Coombs Jr., Printed Circuits Handbook, third edition, 1988, McGraw-Hill Book Company, New York.
  • the photopolymerizable compositions according to the present invention are particularly advantageous as permanent additive resists used in the step of generating a desired metallization pattern, the use of the instant compositions is not confined to this particular aspect of PWB manufacture.
  • the instant photoresists display generally favourable properties and so are widely utilizable.
  • the photopolymerizable compositions as described hereinbefore can advantageously be used to protect selected areas of the conductive pattern of a printed wiring board from the action of molten solder.
  • composition of the instant invention may also be used in the subtractive manufacture of printed wiring boards.
  • Subtractive manufacture involves the process step of etching away copper from a copper-laminated substrate in order to define a conductive pattern.
  • the composition of the instant invention is particularly suitable in defining said pattern (which is protected from the etchant by the photoresist coating.
  • the invention also pertains to a printed wiring board comprising a substrate covered partially with a conductive metal pattern and partially with a polymeric permanent plating resist, the permanent plating resist being a cured photopolymerizable composition of the type described hereinbefore, in any embodiment.
  • EpTAIC - partially epoxidated TAIC mixture
  • TGIC 6.6 t% triglycidyl isocyanurate
  • DiGIC 17.2 wt% DiGIC
  • Mo 37.6 wt% Mo ' noGIC
  • 26.7 wt% TAIC 26.7 wt% TAIC
  • TAC prepolymer having a viscosity of 2700 cP, in a solvent-free mixture of 39 wt% of prepolymer having Mw 58550 and Mn 5453, and 61 wt% TAC monomer.
  • TMPTA trimethylol propane tri acrylate
  • Photo-initiator (c) was added to the homogeneous mixture formed under (3) to form a photopolymerizable composition.
  • the photopolymerizable composition formed under (4) was coated onto a support material of either glass, FR-4 (epoxy resin) board, or PET-film, dried for 5 minutes at room-temperature in a so-called "forced-dry” oven and for 30 minutes at 50°C, and the resulting tacky photopolymerizable coating was covered with a protective PET layer.
  • the light source used is a Philips HOK-6 80 W/cm (moving belt) mercury lamp.
  • the UV bump is carried through using a Philips HPK 125 W (static) mercury lamp.
  • the viscosity of the photoresist formulation was measured with a
  • Brookfield viscometer at 21°C in mPa.s.
  • the cure speed was examined by passing the photoresist-coated substrate under a 80 W/cm lamp at four different belt speeds (hence four different irradiation times).
  • the photoresist was irradiated through the protective PET layer, which was removed 20 minutes thereafter. Reported is the scratch- and/or tackfree state of the photoresist after irradiation and post-exposure hold time.
  • a photoresist which upon being touched did not display any stickiness was considered tackfree.
  • a photoresist which could not be scratched with a fingernail edge was considered scratchfree, and cured.
  • the Persoz hardness was measured on samples having glass as the support layer, using standard Persoz hardness equipment. The hardness of the samples was measured twice, viz. after initial exposure and hold time, and after the complete curing procedure.
  • Solvent resistance after the initial as well as the final cure was determined by placing samples having glass as the support layer in a solvent during 1 hour at 21°C A sample was considered solvent- resistant if the coating layer did not show any visible change, such as deterioration, curling, swelling or lift-up from the substrate.
  • Exampl e I Solvent resistance after the initial as well as the final cure was determined by placing samples having glass as the support layer in a solvent during 1 hour at 21°C A sample was considered solvent- resistant if the coating layer did not show any visible change, such as deterioration, curling, swelling or lift-up from the substrate.
  • Example I a photopolymerizable composition was formed in accordance with the procedure given above, in the following manner:
  • TAC trimethylolpropane triacrylate
  • Example I As Example I, except that 5 wt% Irgacure 651 (c) was used and further 1.0 wt% of Sunfast Blue pigment (f) added.
  • Hot alkali resistance is tested at a pH of 12, a temperature of 82°C, and for a period of 24 hours.
  • compositions are made up as fol lows, with the amounts of ingredients expressed in weight percentages:
  • thermogravimetric analysis TGA
  • a low content of volatile substances is of importance with regard to soldering.
  • the "solder shock” (280°C) to which printed wiring boards are usually subjected may lead to blistering in the case of a high volatiles content.
  • Samples I-X as well as a PARl sample were subjected to a test described in US 4,601,970, according to which cured films are immersed in a methylene blue solution for 5 minutes, after having been subjected to hot alkali for 24 hours.
  • the samples in accordance with the invention did not or hardly display any blue coloration, which demonstrates that the samples where well resistent towards hot alkali.
  • PARl subjected to hot alkali displayed a deep blue colour, which PARl not subjected to hot alkali did not.
  • a conventional adhesive-coated FR4 epoxy-glass laminate rendered suitable for additive plating was provided with photopolymerizable composition prepared (essentially according to the procedure used in the previous Examples) from the following ingredients. The amounts expressed are weight percentages. a. l TAC 17.0 a.2 TMPTA 14.4 a.2 Diacryl 101 29.4 b.l epikote 828 LV/EL 12.8 b.2 maleic anhydride 5.3 c. irgacure 651 4.7 d. PMMA 16.3 e. Dowanol PMA/o-xylene 50.0 f. Holcolest pigment green EP 91719) 0.1
  • the photopolymerizable composition was applied to the adhesive laminate by meter-bar coating.
  • the wet coated layer was dried by heating to 60°C for 30 minutes.
  • the dry film thickness was 25-30 ⁇ m.
  • a polyethylene terephthalate cover sheet of 23 ⁇ m thickness was applied over the dried layer.
  • the coated laminate was subjected to exposure to UV irradiation through a phototool. After a holdtime of 30 minutes the latent image was developed in a 1/1 mixture of Dowanol PMA/o-xylene. The image exhibited excellent resolution and side-wall geometry. Subsequently the image was thermally cured at 150°C for 1 hour. After cooling to room temperature the image was subjected to UV irradiation for 3 minutes using a Philips HPK 125 W lamp.
  • the imaged surface was degreased by washing with a warm soapy solution having a pH of about 10, followed by a water rinse.
  • the exposed adhesive areas were adhesion promoted in a hot solution of chrome sulphuric acid and sodium fluoride, followed by neutralisation in a sodium bisulphite solution and rinsing in water.
  • the laminate was then immersed in an electroless copper plating solution (Kollmorgen PCK 570, pH 12, temperature 70°C). In about one day's time this resulted in deposition of a copper circuit pattern.
  • the photoimaged resist layer was unaffected (no leachables, no extraneous copper, no nodules).
  • Example XI The photopolymerizable composition of Example XI was applied to a conventional adhesive-coated FR4 epoxy-glass laminate.
  • the conventional laminate was not rendered suitable for additive plating, i.e. the adhesive coating did not contain catalyst for electroless plating.
  • the surface of the cured coating was roughened and subsequently degreased by washing with a warm soapy solution having a pH of about 10, followed by a water rinse.
  • the laminate After 30 seconds of immersion in an aqueous 1% hydrochloric acid solution the laminate was placed in a colloidal solution of palladium chloride. After soaking for 10 minutes the laminate was washed with demineralized water and then immediately placed in an electroless copper-plating bath (Shipley Cuposit ® 328 Q) .
  • composition was prepared as a 40% solution in Dowanol PMA.
  • composition was coated onto glass, thickness 26 ⁇ m. After drying the coating was tackfree.
  • composition displayed a poor curing speed.
  • the " composition was ten times less sensitive than the photoresist of the present invention.
  • the final composition displayed a poor hot alkali resistance.

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Abstract

Composition photopolymérisable comportant un mélange de monomères réticulants interpénétrés et un agent d'amorçage photochimique, lesquels monomères réticulants interpénétrés comportent des composés éthyléniquement insaturés pouvant former un réticulat polymérique, ainsi qu'un mélange pouvant former un réticulat de résine époxy. Le réticulat polymérique est formé, au moins en partie, de composés allyliques. Le réticulat polymérique et le réticulat de résine époxy sont essentiellement liés l'un à l'autre par l'intermédiaire d'un composé possédant à la fois un groupe fonctionnel éthyléniquement insaturé et un groupe fonctionnel pouvant réagir avec au moins un des ingrédients du réticulat de résine époxy. De préférence, ledit composé est un réticulant éthyléniquement insaturé d'époxy tel que l'anhydride maléique. La composition photopolymérisable peut également comporter des monomères vinyliques photopolymérisables, un liant filmogène, un solvant, des pigments et d'autres additifs, et est utilisée notamment comme résist de placage additif ou, au cas où des catalyseurs additifs seraient utilisés, comme résist adapté au placage sans courant.
PCT/EP1992/002332 1991-12-06 1992-10-09 Composition photopolymerisable contenant des reticulats polymeriques epoxy et allyliques lies les uns aux autres WO1993011465A1 (fr)

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EP91203191.1 1991-12-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1689909B1 (fr) * 2003-12-05 2017-10-11 CIT Technology Limited Formation de couches solides sur des substrats

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0246467A2 (fr) * 1986-04-28 1987-11-25 Tokyo Ohka Kogyo Co., Ltd. Composition de résine photosensible et son utilisation
EP0270945A2 (fr) * 1986-12-02 1988-06-15 E.I. Du Pont De Nemours And Company Composition photosensible ayant une adhésion améliorée, objets et procédés
EP0359216A1 (fr) * 1988-09-13 1990-03-21 AMP-AKZO CORPORATION (a Delaware corp.) Photorésistant formateur d'image permanent
EP0366333A2 (fr) * 1988-10-28 1990-05-02 W.R. Grace & Co.-Conn. Résines pour masque de soudure à stabilité modifiée
EP0417837A1 (fr) * 1989-09-15 1991-03-20 Akzo Nobel N.V. Réseau interpénétré à liaisons chimiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0246467A2 (fr) * 1986-04-28 1987-11-25 Tokyo Ohka Kogyo Co., Ltd. Composition de résine photosensible et son utilisation
EP0270945A2 (fr) * 1986-12-02 1988-06-15 E.I. Du Pont De Nemours And Company Composition photosensible ayant une adhésion améliorée, objets et procédés
EP0359216A1 (fr) * 1988-09-13 1990-03-21 AMP-AKZO CORPORATION (a Delaware corp.) Photorésistant formateur d'image permanent
EP0366333A2 (fr) * 1988-10-28 1990-05-02 W.R. Grace & Co.-Conn. Résines pour masque de soudure à stabilité modifiée
EP0417837A1 (fr) * 1989-09-15 1991-03-20 Akzo Nobel N.V. Réseau interpénétré à liaisons chimiques

Non-Patent Citations (2)

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Title
PATENT ABSTRACTS OF JAPAN vol. 12, no. 148 (C-493)(2995) 7 May 1988 *
PATENT ABSTRACTS OF JAPAN vol. 6, no. 79 (P-115)(957) 18 May 1982 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1689909B1 (fr) * 2003-12-05 2017-10-11 CIT Technology Limited Formation de couches solides sur des substrats

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