EP0214097B1 - Mélange d'oléfine et de complexe dibenzalacétone-palladium et son utilisation - Google Patents

Mélange d'oléfine et de complexe dibenzalacétone-palladium et son utilisation Download PDF

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EP0214097B1
EP0214097B1 EP86810368A EP86810368A EP0214097B1 EP 0214097 B1 EP0214097 B1 EP 0214097B1 EP 86810368 A EP86810368 A EP 86810368A EP 86810368 A EP86810368 A EP 86810368A EP 0214097 B1 EP0214097 B1 EP 0214097B1
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mixture according
component
mixture
formula
binder
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EP0214097A1 (fr
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Jürgen Dr. Finter
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Novartis AG
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Ciba Geigy AG
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    • 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
    • C23C18/28—Sensitising or activating
    • 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
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the invention relates to a mixture of at least one non-volatile substance with at least one olefinic double bond and a dibenzalacetone-palladium complex and their use for electroless metal deposition.
  • m is preferably a number from 2 to 4 and n is preferably a number from 0 to 10, particularly 0 to 6.
  • group C m H 2m means ethylene , 1,2- or 1,3-propylene or 1,4-butylene.
  • the compounds of the formula I can also be in the form of mixtures of palladium complexes with different meanings of q.
  • q is preferably a rational number from 2 to 3.5.
  • Alkyl and alkoxy groups R 2 and alkyl groups R 3 can be straight-chain or branched. Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl and sec-butyl; Methoxy, ethoxy, n-propoxy, n-butoxy and sec-butoxy.
  • Halogen atoms R 2 are especially bromine and chlorine atoms. If R 2 is aryl, it is, for example, 1- or 2-naphthyl and especially phenyl. Examples of defined aralkyl or alkaryl groups R 2 are benzyl, ⁇ - and ⁇ -phenylethyl, methylbenzyl, tolyl, xylyl and ethylphenyl.
  • R 2 and R 3 each preferably represent a hydrogen atom.
  • R 1 is preferably bonded in the m, m 'and in particular p, p' position and preferably represents H, OH or Compounds of the formula I in which R 1 is H, OH or are particularly preferred represents and R 2 and R 3 are each a hydrogen atom.
  • the compounds of formula I can be prepared by processes known per se [cf. e.g. BJ Chem. Soc. D, 1970, 1065 and U.S. Patent 4,347,232] by using q moles of a compound of Formula II Reacted in the presence of a base and optionally an H donor with a soluble palladium salt.
  • Ri, R 2 , R 3 and q have the meaning given under Formula 1.
  • alkali metal salts of aliphatic monocarboxylic acids can be used. Suitable palladium salts are, for example, PdBr 2 , PdC1 2 and Na 2 PdCl 4 . Na 2 PdCla and especially PdC1 2 are particularly preferably used.
  • the reaction is expediently carried out in an organic solvent which also acts as an H donor.
  • the compounds of the formula II are known or can be prepared in a manner known per se, for example analogously to the process described in US Pat. No. 3,295,974.
  • the weight ratio of component (a) to component (b) in the mixture according to the invention can be 100: 1 to 1:20, preferably 10: 1 to 1:10, particularly 5: 1 to 1: 5 and in particular 3: 1 to 1: 3.
  • Monomeric, oligomeric and polymeric substances which contain at least one olefinic double bond are suitable as component (a). They can be liquid, liquid-viscous or solid. Liquid and liquid-viscous substances are expediently used together with a binder.
  • Component a) can e.g. B. a Cs-C 2 o-alkene, C 5 -C 12 cycloalkene, an olefinically unsaturated alcohol or amide with 3 to 12 C atoms, an olefinically unsaturated carboxylic acid or carboxylic acid derivatives with 3 to 30 C atoms, a polybutadiene or Polyisoprene, an unsaturated polyester or a polymer with olefinic side groups.
  • Component a) is preferably an acrylic acid or methacrylic acid ester or amide, an optionally C 1 -C 4 -alkyl-substituted maleic acid ester, anhydride, imide or amide, an allyl ether or allylamide, a polymaleic acid ester, a polybutadiene or polyisoprene or a polyolefin with dimethylmaleimide groups in page groups.
  • component a) is a polybutadiene or polyisoprene functionalized with amino, hydroxyl or carboxyl groups and having a molecular weight of 5,000-40,000, in particular 10,000-40,000.
  • the alkene preferably contains 5 to 12 carbon atoms and 1 to 3 double bonds. Examples are pentene, pentadiene, hexene, hexadiene, heptene, octene, decene and dodecene.
  • cycloalkene examples include cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclodecene and cyclododecene.
  • Olefinically unsaturated alcohols or amides preferably contain 3 to 6 carbon atoms.
  • they are allyl alcohols and allyamines.
  • Allyl ethers with preferably 4 to 12 C atoms and allyl esters with preferably 5 to 12 C atoms are also suitable.
  • Unsaturated carboxylic acids or carboxylic acid derivatives preferably contain 3 to 18 carbon atoms. It can be mono- or polycarboxylic acids with preferably 1 to 3 carboxyl groups. Examples of such carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, maleic acid, methyl or dimethyl maleic acid, fumaric acid. Suitable derivatives are esters with preferably 1 to 12 carbon atoms in the ester group, amides, anhydrides and imides. The amides and imides can be substituted with C 1 -C 12 alkyl.
  • esters are acrylic acid esters and methacrylic acid esters of alcohols having 1 to 12 carbon atoms and preferably 1 to 6 hydroxyl groups.
  • Suitable alcohols are C 1 -C 12 alkanols, C 2 -Cs alkanediols, trimethylolpropane, pentaerythritol, poly (oxaalkylene) diols with 2 to 6 C atoms in the alkylene group, bisphenols and novolaks.
  • Suitable esters are also the reaction products of glycidyl compounds with (meth) acrylic acid.
  • the polybutadienes and polyisoprenes can be oligomeric or polymeric homo- or copolymers. Suitable monomers for copolymers are especially acrylonitrile and styrene.
  • Suitable unsaturated polyesters are derived in particular from maleic acid and C 2 -C 16 diols.
  • Polymers with olefinic side groups can be, for example, those which have an acrylic or methacrylic group as the side group.
  • examples are e.g. B. esters of polyvinyl alcohol or polyacrylic acid or methacrylic acid, which are esterified with (meth) Acryläureaikandiolmonoestern.
  • Other suitable polymers with an olefinic side group are those which have a maleimidyl group of the formula in which R 'and R "are, for example, independently of one another a hydrogen atom or C 1 -C 4 -alkyl. Such polymers are described, for example, in US Pat. No. 4,079,041.
  • Component (a) can also function as a binder.
  • the mixture according to the invention can also additionally contain a binder.
  • Such mixtures preferably contain 99.8 to 40% by weight, particularly 99 to 60% by weight, in particular 90 to 70% by weight of binder, 0.1 to 30% by weight, particularly 0.5 to 20% by weight %, in particular 5 to 15% by weight of component (a), and 0.1 to 30% by weight, particularly 0.5 to 20% by weight, in particular 5 to 15% by weight of component ( b).
  • Preferred binders are e.g. B. an epoxy resin, an unsaturated polyester, a polyacrylate or methacrylate, a polyimide, a polyurethane, a polyolefin, a polyamide or a polyester.
  • the binder (c) is particularly preferably an epoxy resin or an epoxy resin mixture with (d) a heat-activatable hardener and / or a curing catalyst.
  • epoxy resins (c) come especially those with an average of more than one to a heteroatom, e.g. B. to an S and preferably to an O or N atom, bonded group of formula III into consideration, where Q and Q 2 each represent a hydrogen atom and 0 1 represent a hydrogen atom or a methyl group or 0 and 0 2 together represent -CH 2 CH 2 - or -CH 2 CH 2 CH 2 - and 0 1 represent a hydrogen atom.
  • a heteroatom e.g. B. to an S and preferably to an O or N atom, bonded group of formula III into consideration, where Q and Q 2 each represent a hydrogen atom and 0 1 represent a hydrogen atom or a methyl group or 0 and 0 2 together represent -CH 2 CH 2 - or -CH 2 CH 2 CH 2 - and 0 1 represent a hydrogen atom.
  • polyglycidyl and poly ( ⁇ -methylglycidyl) esters which are derived from aliphatic, cycloaliphatic or aromatic polycarboxylic acids.
  • suitable polycarboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimerized or trimerized linoleic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, phthalic acid, isoic acid and talsoic acid.
  • polyglycidyl and poly ( ⁇ -methylglycidyl) ethers which are obtained by reacting a compound containing at least two alcoholic and / or phenolic hydroxyl groups per molecule with epichlorohydrin or with allyl chloride and subsequent epoxidation with peracids.
  • Suitable polyols are e.g. B. ethylene glycol, diethylene glycol, poly (oxyethylene) glycols, propane-1,2-diol, poly (oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly (oxytetramethylene) glycols, pentane 1,5-diol, hexane-2,4,6-triol, glycerin, 1,1,1-trimethylolpropane, pentaerythritol and sorbitol; Resorcite, quinite, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane and 1,1-bis (hydroxymethyl) cyclohex-3-ene; N, N-bis (2-hydroxyethyl) aniline and 4,4'-bis (2-hydroxyethylamino) diphenylmethane; Resorcinol, hydroquinone, bis (4-hydroxy
  • Products obtained by dehydrochlorination of reaction products from epichlorohydrin and amines with at least two amine hydrogen atoms are suitable as poly (N-glycidyl) compounds.
  • Suitable amines are e.g. B. aniline, n-butylamine, bis (4-aminophenyl) methane, 1,3- and 1,4-xylylenediamine, 1,3- and 1,4-bis (aminomethyl) cyclohexane and bis (4-methylaminophenyl) methane .
  • Triglycidyl isocyanurate N, N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethylene urea and 1,3-propylene urea, or hydantoins, such as 5,5-dimethylhydantoin, are further suitable compounds of this type.
  • Poly (S-glycidyl) compounds are e.g. B. the di-S-glycidyl derivatives of dithiols, such as ethane-1,2-dithiol and bis (4-mercaptomethylphonyl) ether.
  • Examples of epoxy resins with one or more groups of the formula III, in which Q and Q 2 together represent a group -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -, are bis (2,3-epoxycyclopentyl) ether, 2 , 3-epoxycyclopentylglycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methyicyclohexane carboxylate and 2- (3rd , 4-epoxy) cyclohexyl-5,5-spiro (3 ', 4'-epoxy) cyclohexane-dioxane.
  • component (c) optionally advanced diglycidyl ethers of dihydric phenols, especially 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis ( 4-hydroxyphenyl) methane, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane, polyglycidyl ether of novolaks, or tetraglycidylated 4,4'-diaminodiphenylmethane.
  • 2,2-bis (4-hydroxyphenyl) propane 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane
  • bis ( 4-hydroxyphenyl) methane bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane
  • polyglycidyl ether of novolaks or tetraglycidylated 4,4'-diaminodiphenylme
  • any desired epoxy resin hardener such as, for example, is suitable as hardener (d) for epoxy resins.
  • Suitable polycarboxylic acids and their anhydrides are e.g. B. phthalic anhydride, tetrahydro- and hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methylenendomethylentetrahydrophthal Acidanhydrid, endomethylenetetrahydrophthalic anhydride, Hexachlorendomethylentetrahydrophthalcic acidanhydrid, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, succinic anhydride, nonenylsuccinic anhydride, dodecenylsuccinic anhydride, polysebacic and polyazelaic and belonging to the above-mentioned anhydrides, acids ..
  • polyamines which are suitable as curing agents are aliphatic, cycloaliphatic, aromatic and heterocyclic polyamines, such as ethylenediamine, propane-1,2-diamine, propane-1,3-diamine, N, N-diethylethylene diamine, hexamethylene diamine, Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N- (2-hydroxyethyl) -, N- (2-hydroxypropyl) - and N- (2-cyanoethyl) diethylenetriamine, 2,2,4- and 2,4,4-trimethylhexane-1, 6-diamine, m-xylylenediamine, N, N-dimethyl and N, N-diethylpropane-1,3-diamine, bis (4-amino-cyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2 , 2-bis (4-amino-3-methoxycyclohex
  • Suitable polyaminoamides are e.g. B. those made from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids.
  • adducts of amines and polyepoxides such as adducts of amines and polyepoxides such.
  • Possible polyol hardeners (d) are, in particular, mono- or polynuclear aromatic polyols, including novolaks, such as resorcinol, hydroquinone, 2,6-dihydroxytoluene, pyrogallol, 1,1,3-tris (hydroxyphenyl) propane, bis (4- hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone and 4,4'-dihydroxybiphenyl as well as novolaks made from formaldehyde or acetaldehyde and phenol, chlorophenol or alkylphenols with up to 9 carbon atoms in the Alkyl, especially cresol and phenol novolaks.
  • novolaks such as resorcinol, hydroquinone, 2,6-dihydroxytoluene, pyrogallol, 1,1,3-tris (hydroxyphenyl) propane, bis (4- hydroxyphenyl
  • Preferred hardeners are polycarboxylic anhydrides such as norbornene dicarboxylic anhydride, tetrahydro-, hexahy Dro- and methyltetrahydrophthalic anhydride, and aromatic polyamines, especially bis (4-aminophenyl) methane, bis (4-aminophenyl) sulfone and m- or p-phenylenediamine.
  • polycarboxylic anhydrides such as norbornene dicarboxylic anhydride, tetrahydro-, hexahy Dro- and methyltetrahydrophthalic anhydride
  • aromatic polyamines especially bis (4-aminophenyl) methane, bis (4-aminophenyl) sulfone and m- or p-phenylenediamine.
  • the hardeners (d) are used in the amounts customary in epoxy resin technology, expediently in amounts such that there are about 0.7 to 1.5 equivalents of functional groups of the hardener (d) for one equivalent of OH or glycidyloxy groups.
  • Compounds known per se can also be used as curing catalysts (d). Examples include: complexes of amines, especially tertiary amines, such as monoethylamine, trimethylamine and octyldimethylamine, with boron trifluoride or boron trichloride, mono-esters of aspartic acid, such as 4-methyl N- (3-dimethylamine-propyl) -aspartic acid, and in particular optionally substituted imidazoles such as imidazole, benzimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-vinylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1- (2,6-dichlorobenzoyl) -2-phenylimidazole and 1- (2,4,6-trimethylbenzoyl) -2-phenylimidazole. Imidazoles, especially 2-phenylimidazole
  • the mixtures according to the invention may contain curing accelerators in addition to component (d).
  • Suitable accelerators are e.g. B. tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, hexamethylenetetramine or 1,6-bis (dimethylamino) hexane; aromatic carbonates, such as diphenyl carbonate, and urea derivatives, such as N-4-chlorophenyl-N ', N'-dimethylurea (monuron), N-3-chloro-4-methylphenyl-N', N'-dimethylurea (chlorotoluron), N- (2-hydroxyphenyl) -N ', N'-dimethylurea and N- (2-hydroxy-4-nitrophenyi) -N, N-dimethyl urea.
  • Tertiary amines, especially benzyldimethylamine are preferred as the curing accelerator (d
  • the component (d) and the accelerator are in the usual effective, i.e. H. sufficient amounts are used for curing the mixtures according to the invention.
  • the ratio of component (d) to accelerator depends on the type of compounds used, the required curing rate and the properties desired in the end product and can be easily determined by a person skilled in the art of epoxy resin curing.
  • the mixtures according to the invention can also contain other known customary additives.
  • additives are pigments, dyes, reinforcing materials, such as glass fibers, flame retardants, reactive thinners for the epoxy resins, such as phenyl and cresyl glycidyl ethers, butanediol diglycidyl ether and hexahydrophthalic acid diglycidyl ether, antistatic agents, leveling agents, anti-caking agents, anti-caking agents, coupling agents.
  • the mixtures according to the invention depending on the properties, for. B. Application as adhesives or for the production of moldings, hardened products, especially castings, laminates and thin coatings (films) and self-supporting films. Common shaping processes are used here, e.g. B. injection molding, extrusion or compression molding. To apply coatings to surfaces, the coating according to the invention is expediently dissolved and, after coating, the solvent is removed using customary methods. Suitable solvents, which can be used alone or in mixtures, are e.g. B.
  • ketones such as dimethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, isophorone, methoxyhexanone, acetonylacetone, acetophenone, benzyl ethyl ketone, 3,3,5-trimethylcyclohexanone, mesityl oxide; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, methylene bromide, bromochloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachiorethane.
  • ketones such as dimethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, isophorone, methoxyhexanone
  • Alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, monoalkylated glycols such as methyl glycol, ethyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol, triethylene glycol monomethyl or ethylene, monoethyl, or ethylene, monoethyl, or ethylene, monoethyl, or ethylene, monoethyl, mono- or ethylene, monoethyl, mono- or ethylene, monoethyl, or monoethyl, monoethyl, or ethylene, monoethyl, monoethyl, monoethyl, or ethylene, monoethyl, monoethyl, monoethyl, such as their
  • Suitable carrier materials are common materials, which are preferably electrically non-conductive. Examples are paper, wood, plastics, glass, ceramics and semiconductors.
  • the mixtures according to the invention which additionally contain an epoxy resin as a binder, are generally cured by heating to temperatures between 80 and 200 ° C., particularly 100 and 180 ° C.
  • the compounds of formula 1 with OH or glycidyl groups are polymerized in undestroyed form and finely divided into the network of the hardened products, without the mechanical properties of the hardened products being adversely affected thereby.
  • the mixtures according to the invention release finely dispersed elemental zero-valent palladium when irradiated with actinic light, especially UV light.
  • Suitable light sources are, for example, xenon lamps, argon lamps, tungsten lamps, carbon arcs, metal halide and metal arc lamps, such as low-pressure, medium-pressure and high-pressure mercury lamps, argon ion lasers, frequency-doubled Nd-YAG lasers (yttrium aluminum garnet) and UV lasers.
  • the irradiation can also be carried out through a photomask. This gives samples of zero-valent palladium.
  • the coatings or patterns obtained after irradiation with actinic light are particularly suitable for electroless metal deposition, whereby electrically conductive metallic coatings or patterns are obtained.
  • Electroless metal deposition can be carried out using metallization baths known per se and by customary methods be performed. Examples of suitable metals are copper, nickel, cobalt, silver and tin or cobalt-phosphorus and cobaft-nickel alloys.
  • Another object of the invention is the use of the mixtures according to the invention for electroless metal deposition and a method for the metallization of surfaces of an electrically non-conductive material by electroless metal deposition, characterized in that a shaped body, a layer of the mixture according to the invention in the form of a self-supporting film or a a layer applied according to the invention is irradiated and thereby produces zero-valent palladium, and then a metal layer is applied by electroless metal deposition in a metal deposition bath.
  • patterns with high resolution can be achieved.
  • Such products can e.g. B. can be used as printed circuits.
  • a precipitate is formed which is filtered off under argon and washed once with 100 ml of methanol, three times with 100 ml of water and twice with 100 ml of methanol. The product is then dried at 50 ° C in a vacuum. To completely remove residual dibenzalacetone-bis-p, p'-diglycidyl ether, the crystals are suspended again in 700 ml of methanol and filtered off under argon. It is then dried in vacuo. 100.7 violet crystals (97% of theory) are obtained. Decomposition range: 120 - 160 ° C. The analysis gives a value of 3.2 for q.
  • Example 1 25 g of a polymer of 80 mol% of N (5-methyl-3-oxa-4-oxo-hexan-5-yl) dimethylmaleinimide (X) and 20 mol% of ethyl acrylate are dissolved in 140 ml of cyclohexanone and mixed with 7.11 g of complex II added. A 25 ⁇ m thick layer is produced on a polyester film from the solution obtained and the solvent is removed in a forced air oven. Then irradiate under a photomask for 100 seconds with a 440 W medium-pressure mercury lamp.
  • Example 2 Example 1 is repeated, but with complex I instead of complex II. The same result is obtained.
  • Example 3 Example 1 is repeated. After exposure, development is also carried out in 1,1,1-trichloroethane. A relief image is obtained from the photopolymerized polymer X, which is copper-plated by treatment in a copper deposition bath.
  • Example 4 0.75 g of complex I are mixed with 5 g of a bisphenol A diglycidyl ether (bisphenol A diglycidyl ether (epoxide equivalent weight 0.69 mol epoxide / kg)), 0.75 g cis polybutadiene (Mg - 25,000 daltons) Functionalized carboxyl groups) and 0.75 g of norbornenedicarboxylic anhydride dissolved in 15 ml of cyclohexanone. From this solution, 15 ⁇ m thick films are applied to a polyester film, dried in a forced air oven at 80 ° C. for 1 hour and cured at 110 ° C. for 3 hours. The cured film is irradiated with a 5 kW mercury lamp under a photomask for 200 seconds. After treatment in the copper plating bath according to Example 1, a shiny copper image is obtained.
  • a bisphenol A diglycidyl ether bisphenol A diglycidyl ether (epoxide equivalent weight 0.69 mol

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Claims (19)

1. Mélange contenant
a) au moins une substance non volatile comportant au moins une double liaison oléfinique, et
b) au moins un complexe de palladium de formule I:
Figure imgb0014
dans laquelle
R1 représente HO-(-CmH2m-O-)-n. où m est un nombre valant 2 à 6 et n est un nombre valant 0 à 20, -O-
CH2CHOHCH2OH ou
Figure imgb0015
, ou bien R1 a, indépendamment, le sens de R2, et
R2 représente un atome d'hydrogène, un groupe alkyle en Ci à C4, un groupe alcoxy en Ci à C4, un atome d'halogène,
un groupe aryle en Ce à C10, un groupe aralkyle en C7 ou Ce ou un groupe alcaryle en C7 ou C8,
R3 représente un atome d'hydrogène ou un groupe alkyle en Ci à C4, ou bien les deux R3 forment ensemble une chaîne polyméthylénique ayant 2 à 4 atomes de carbone, et
q est un nombre rationnel valant 1 à 3,5.
2. Mélange selon la revendication 1, dans lequel, dans la formule I, q est un nombre rationnel valant 2 à 3,5.
3. Mélange selon la revendication 1, dans lequel, dans la formule I, R2 et R3 représentent chacun un atome d'hydrogène.
4. Mélange selon la revendication 1, dans lequel, dans la formule I, R1 est fixé en position p,p'.
5. Mélange selon la revendication 1, dans lequel, dans la formule I, R1 représente H, -OH ou
Figure imgb0016
6. Mélange selon la revendication 1, dans lequel le rapport pondéral du composant (a) au composant (b) se situe entre 100: 1 et 1 : 20.
7. Mélange selon la revendication 1, dans lequel le composant a) est un alcène en C5 à C2o, un cycloalcène en à C12, un alcool ou amide à insaturation oléfinique comportant 3 à 12 atomes de carbone, un acide carboxylique ou dérivé d'acide carboxylique à insaturation oléfinique comportant 3 à 30 atomes de carbone, un polybutadiène ou un polyisoprène, un polyester insaturé ou un polymère comportant des groupes oléfiniques latéraux.
8. Mélange selon la revendication 7, dans lequel le composant a) est un ester ou amide d'acide acrylique ou d'acide méthacrylique, un ester, anhydride, imide ou amide d'acide maléique portant éventuellement comme substituant un groupe alkyle en Ci à C4, un éther-oxyde allylique ou un amide d'allyle, un poly(ester d'acide maléique), un polybutadiène ou un polyisoprène ou bien une polyoléfine comportant des groupes diméthylmaléimide comme groupes latéraux.
9. Mélange selon la revendication 7, dans lequel le composant a) est un polybutadiène ou polyisoprène, comportant un ou deux groupes amino, hydroxyles ou carboxyles comme groupes fonctionnels et ayant un poids moléculaire de 5 000 à 40 000.
10. Mélange selon la revendication 1, caractérisé en ce qu'il contient en outre un liant c).
11. Mélange selon la revendication 10, caractérisé en ce qu'il contient 0,1 à 30 en poids du composant a), 0,1 à 30 en poids du composant b) et 99,8 à 40 % en poids de liant c).
12. Mélange selon la revendication 10, dans lequel le liant c) est un polymère thermodurcissable ou thermoplastique.
13. Mélange selon la revendication 10, dans lequel le liant c) est une résine époxyde, un polyester insaturé, un polyacrylate ou polyméthacrylate, un polyimide, un polyuréthanne, une polyoléfine, un polyamide ou un polyester.
14. Mélange selon la revendication 11, dans lequel le liant c) contient une résine époxyde ou un mélange de résines époxydes ainsi que d) un durcisseur activable par la chaleur et/ou un catalyseur de durcissement.
15. Mélange selon la revendication 14, dans lequel la substance c) contenant les groupes époxydes est un éther-oxyde diglycidylique de bisphénol A ayant un poids moléculaire moyen de 600 à 5 000 daltons, et le durcisseur d) est un anhydride d'acide polycarboxylique ou une polyamine aromatique.
16. Procédé pour la métallisation de surfaces d'une matière non conductrice de l'électricité, par dépôt d'un métal sans passage d'un courant électrique, procédé caractérisé en ce qu'on soumet un objet moulé, une couche du mélange selon la revendication 1 sous forme d'une pellicule se supportant d'elle-même ou une couche selon la revendication 1, appliquée sur une matière de support, à irradiation que l'on obtient ainsi du palladium de valence nulle, puis l'on applique une couche de métal, par dépôt de métal sans passage de courant électrique dans un bain de dépôt de métal.
17. Procédé selon la revendication 16, dans lequel on effectue l'irradiation à travers un photomasque (ou photoréserve) et l'on obtient une image ou un tracé lors de la métallisation.
18. Utilisation du mélange selon la revendication 1 pour un dépôt de métal sans passage d'un courant électrique.
EP86810368A 1985-08-23 1986-08-18 Mélange d'oléfine et de complexe dibenzalacétone-palladium et son utilisation Expired EP0214097B1 (fr)

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US5310580A (en) * 1992-04-27 1994-05-10 International Business Machines Corporation Electroless metal adhesion to organic dielectric material with phase separated morphology
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US5032488A (en) 1991-07-16
DE3667800D1 (de) 1990-02-01

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