Classifications

• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/145—Infrared

Definitions

• the invention relates to polymer compositions in which a dibenzalacetone-palladium complex is dissolved, a process for electroless metal deposition on substrate surfaces and the use of said polymer compositions in the production of metallized surfaces or of conductive patterns on substrate surfaces.
• EP-A 125 617 describes mixtures of polymers and organometallic complexes. Pd-II complexes but no Pd ° complexes, for example dibenzalacetone-palladium complexes, are mentioned. Pd metal can be deposited from such Pd-II complexes either reductively or by heating to relatively high temperatures. The thermally activated polymer surfaces are suitable according to EP-A 125 617
• R 1 , R 2 , R 4 and R 5 as alkyl and alkoxy groups can be straight-chain or branched. Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert.
• R 1 , R 2 , R 4 and R 5 carry non-polar substituents, for example C 1 -C 4 alkyl or alkoxy radicals, as substituted phenyl. Examples include methyl, ethyl or methoxy.
• Examples of preferred substituted phenyl radicals R 1 , R 2 , R 4 and R 5 are o-, m- or p-tolyl, o-, m- or p-methoxyphenyl or 2,3-, 2,4-, 2,5 -, 2,6- or 3,5-dimethylphenyl.
• m is preferably a number from 2-4 and n is preferably a number from 0-10, particularly preferably 0-6.
• group C m H 2m means ethylene, 1,2- or 1,3-propylene or 1,4-butylene.
• the halogen atom R 2 can be fluorine, chlorine, bromine or iodine. Chlorine and bromine, in particular chlorine, are preferred.
• R 2 is a glycidyl ether radical, it is preferably a group of the formula II wherein R 6 and R 8 each represent a hydrogen atom, where R 7 is then a hydrogen atom or a methyl group, or wherein R 6 and R 8 together represent -CH 2 CH 2 -, where R 7 is then a hydrogen atom.
• R 2 as glycidyl ether radical is preferably a group of the formula III
• R 3 as C 1 -C 4 -alkyl is preferably straight-chain. Examples of such radicals are methyl, ethyl, propyl or butyl, but particularly preferably methyl.
• R 3 is preferably hydrogen.
• R 3 groups together form a C 2 -C 4 polymethylene chain, these are, for example, ethylene, trimethylene and tetramethylene.
• R 4 and R 5 are preferably hydrogen.
• the compounds of the formula can also be in the form of mixtures with different meanings of q.
• q is preferably 2 to 3.5.
• compositions containing compounds of the formula 1 in which R 1 is hydrogen, R 2 is C 1 -C 12 alkyl, C 1 -C 4 alkoxy, halogen or a glycidyl ether radical are preferred, R 3 is hydrogen and q is a number from 2 to 3, 5 is.
• compositions containing compounds of the formula I in which R 1 is hydrogen, R 2 is C 1 -C 5 alkyl, in particular isopropyl, R 3 is hydrogen and q is a number from 2 to 3.5 are particularly preferred.
• the groups R 2 are preferably each in the p-position.
• the palladium complexes of the formula dissolve in high concentrations in many commercially available polymers.
• the polymers can be soluble or insoluble in organic solvents; i.e. linear or cross-linked polymers.
• the cross-linked polymer precursors must be soluble in organic solvents.
• the solvents used are those which do not decompose the palladium complex I, preferably apolar organic solvents.
• solvents examples include aliphatic or aromatic hydrocarbons, such as n-hexane, n-heptane, cyclohexane, benzene, toluene or xylene, ethers, such as di-n-butyl ether, diethyl ether, diphenyl ether, 1,4-dioxane, anisole tetrahydrofuran , diethylene glycol diethyl ether, Ethylenglykoldimethyl ether or triethylene glycol dimethyl ether, halogenated hydrocarbons such as carbon tetrachloride, chlorobenzene, bromobenzene, chloroform, dichloromethane or 1,2-dichloroethane, ketones such as cyclohexanone, methyl ethyl ketone, acetophenone or acetone, and esters such as ethyl acetate.
• the respective polymers are considered soluble if they dissolve in the solvent in question at room temperature to at least 1 mg / l, preferably at least 10 mg / l.
• the polymers preferably have a glass transition temperature of more than 90 ° C.
• the polymer component in the mixtures according to the invention must be free from olefinic double bonds or conjugated, non-aromatic double bond systems.
• the palladium complex is selected such that it is not polymerized into the polymer matrix in the subsequent crosslinking step.
• compositions containing as component a) a polymer (mixture) which is soluble in organic solvents are preferred.
• compositions in which the polymer is selected from the group consisting of polystyrene, polyvinyl chloride, polycarbonate, polyarylate and polyimide soluble in organic solvents are particularly preferred.
• compositions according to the invention may equally well contain, as component a), a crosslinked or crosslinkable polymer, for example an epoxy resin.
• a crosslinked or crosslinkable polymer for example an epoxy resin.
• the palladium complex should be chosen so that it is not polymerized into the polymer structure, but only remains dissolved in it.
• the invention therefore preferably relates to compositions as defined above, containing as component a) an epoxy resin.
• epoxy resins which are suitable for the construction of crosslinked substrates and of hardeners for these resins can be found in Ullmann's Encyclopedia of Industrial Chemistry, Volume 10, 2. 563-580 (4th edition, Verlag Chemie, Weinheim / Bergstr .; 1975).
• the proportion of dibenzalacetone-palladium complex of the formula 1 in the compositions according to the invention is generally 0.1-25% by weight, preferably 0.5-10% by weight, based on the total mixture.
• 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, antistatic agents, flow control agents, release agents, adhesion promoters, antioxidants and light stabilizers.
• the mixtures according to the invention can also contain electrically conductive fillers c), expediently in amounts of 1-90% by weight, particularly 40-80% by weight, based on the total weight of the mixture, components a) to c) add up to 100% by weight.
• electrically conductive fillers are those of an organic or inorganic type, e.g. Carbon black and graphite or metals of groups Vb, Vlb, VIII and Ib of the periodic table, alloys and salts thereof, such as halides, oxides and sulfides.
• suitable metals and metal compounds are: vanadium, niobium, tantalum, molybdenum, tungsten, copper, noble metals, such as Pt, Pd, Ag and Au, AgPd alloys, silver oxide, silver iodide, copper (il) sulfide, copper (1) iodide, Copper (II) oxide, gold (III) bromide, iodide and oxide, molybdenum (IV) sulfide, niobium (V) chloride and oxide, palladium iodide, palladium oxide, platinum (VI) bromide and chloride, vanadium (III) chloride, vanadium (IV) oxide, tungsten (VI) chloride and oxide.
• Silver, copper, silver / palladium alloys, palladium, platinum, gold, tungsten and molybdenum are preferred.
• Au, Pt AgPd and especially Ag and Cu powder are particularly preferred.
• compositions according to the invention can be prepared in a simple manner by dissolving the polymer or its crosslinkable precursor combined with a suitable crosslinking agent and the complex together and then pouring this solution into films in a manner known per se or applying it to a suitable substrate and optionally then hardens.
• Suitable substrates are common materials, which are preferably electrically non-conductive. Examples include paper, wood, glass, ceramics, semiconductors such as silicon, germanium or gallium arsenide, and in particular plastics, preferably hardened epoxy resins.
• metallic substrates such as aluminum or copper, can also be coated with the mixtures.
• the substrate is coated using customary methods, for example by immersion, brushing and spraying processes, spin coating, cascade casting or curtain casting coating.
• the polymer or its crosslinkable precursor and complex I can be dissolved together in a solvent. However, it is also possible to use mixtures of different solvents or to combine separate solutions of polymer or crosslinkable precursor and complex in different solvents.
• an adhesion promoter can be added to the solution.
• an adhesion promoter you can e.g. use a linear, soluble epoxy polymer.
• the compounds of formula 1 can be prepared by processes known per se (cf., for example, J. Chem.Soc. D, 1970, 1065 and US Pat. No. 4,347,323) by q mol of a compound of formula IV in the presence of a base and optionally an H donor with a soluble palladium salt.
• R 1 , R 2 , R 3 and q have the meaning given under formula I.
• Alkali metal salts of aliphatic monocarboxylic acids can be used as bases.
• Suitable palladium salts are, for example, PdBr 2 , PdCl 2 and Na 2 PdCl 4 .
• Na 2 PdC 1 4 and especially PdCl 2 are particularly preferably used.
• the reaction is expediently carried out in an organic solvent which also acts as an H donor. Suitable for this purpose are, for example, alkanols with up to 6 carbon atoms, especially ethanol and particularly preferably methanol.
• the compounds of the formula IV can be prepared in a manner known per se, for example analogously to the process described in US Pat. No. 3,295,974.
• composition according to the invention can be used for the electroless metallization of plastics or for the production of structured metal surfaces on plastics.
• the activation for the electroless metal deposition is carried out by heating to temperatures above 100 ° C., preferably to 100-250 ° C., particularly preferably to 150-200 ° C.
• the heating can be carried out, for example, by annealing the sample or by irradiation with IR radiation.
• Sources such as IR lasers, or the IR component of actinic radiation sources (for example xenon lamps, argon lamps, tungsten lamps, carbon arcs, metal halide and metal arc lamps, such as mercury lamps) take place.
• the temperature treatment releases finely dispersed, catalytically active palladium.
• Irradiation with IR sources can also take place in an image, e.g. by a laser beam that is guided over the surface.
• the annealing process can take between 1 and 60 minutes depending on the temperature; the tempering times are surprisingly very short.
• the Pd ° clusters formed are catalytically active and catalyze the electroless metallization (eg nickel plating, copper plating) of the polymer surface, for example according to the following scheme:
• Electroless metal deposition can be carried out using metallization baths known per se and by customary methods.
• suitable metals are copper, nickel, cobalt, silver, gold and tin or cobalt-phosphorus and cobalt-nickel alloys.
• composition according to the invention in a structured manner to a substrate, for example by means of a screen printing or a selectively controlled spray mist recording method. Suitable recording methods are described for example in DE-OS 3,326,508.
• the structuring can also be carried out using a photoresist.
• a substrate is coated with a photoresist in a manner known per se.
• the palladium complex 1 can either be dissolved in the photoresist or in an underlying polymer substrate, preferably a polymer layer.
• the sample is annealed and immersed in a metallizing bath.
• the metal deposition now takes place either on the structured photoresist or on the polymer substrate structured by the photoresist.
• stage (iii) and (iv) you can switch on a tempering step between stage (iii) and (iv) to pre-harden the exposed photoresist.
• the materials customary in technology can be used as photoresists.
• photoresist also includes olefinically unsaturated compounds. P.S. gives an overview of imaging processes with such varnishes and selected compound classes. Pappas in “UV Curing: Science and Technology", Chapter 9, pp. 230-253 (1973).
• the photoresist must of course be chosen so that a structure created by the irradiation and development step survives the annealing step without major distortions.
• Such systems are known to the person skilled in the art or can be selected using routine methods.
• a radiation-sensitive polymer system is chosen as the photoresist, the polymer having no olefinic double bonds.
• good results can already be achieved with relatively small amounts of the Pd compound.
• less than 10% by weight of the complex of the formula I, based on the polymer solution is sufficient in order to obtain a catalytically active surface after the exposure and tempering step.
• preference is given to using 1-5% by weight of the complex of the formula 1, based on the polymer solution.
• Examples of radiation-sensitive polymer systems with polymers without olefinic double bonds are combination ions of epoxy resins with photoinitiators of cationic polymerization.
• exposure to a predetermined pattern of actinic radiation means both exposure through a photomask that contains a predetermined pattern, such as a slide, and exposure through a laser beam that is moved, for example, computer-controlled, over the surface, and thus Image created.
• actinic radiation When generating images using a photoresist, actinic radiation of 200 to 600 nm is preferably used. Suitable sources of actinic radiation include carbon arcs, mercury vapor lamps, fluorescent lamps with ultraviolet light-emitting phosphors, argon and xenon incandescent lamps, tungsten lamps and photographic floodlight lamps. However, X-rays or electron beams as well as high-energy radiation can also be used.
• developers can take place, for example, with water, aqueous or aqueous-organic solutions of a base or acid, organic solvents or solvent mixtures.
• Another object of the invention is the use of the mixtures according to the invention for electroless metal deposition, in particular for producing electrically conductive patterns on plastic surfaces.
• patterns according to the invention patterns with high resolution can be achieved.
• Such products can be used, for example, as printed circuits.
• Example 1 Tris (dibenzalacetone-p, p'-diglycidyl ether) palladium.
• 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 g of violet crystals (97% of theory) are obtained. Decomposition range: 120-160 ° C. The analysis gives a value of 3.2 for q.
• Example 2 Tris (p, p'-diisopropyldibenzalacetone) palladium.
• Example 3 Bis (dibenzalacetone) palladium.
• Examples BE One works as described in example A.
• the working conditions of the experiments AE are described in the following table.
• Well-adhering nickel or copper coatings are obtained in each case.
• Example F An epoxy resin plate (60x40x2mm) is coated with a 50 ⁇ m thick polymer film of the composition according to Example C. After the solvent has evaporated, the plate 6 min. heated to 170 ° C and then immersed in one of the nickel plating baths described in Example A. The surface is covered with a well-adhering nickel film.
• Example G Execution as described in Example F. A glass plate is used as the substrate.
• Example H Execution as described in Example F. An aluminum plate is used as the substrate.
• Example 1 0.25 g of the complex according to Example 1 is dissolved in 20 g of 1,2-dichloroethane in a solution of 5 g of a linear polyepoxide * ). With this solution a 50 ⁇ m thick polymer film is produced on an epoxy resin plate (60x40x2mm). After the solvent has evaporated, the coated epoxy resin plate is 6 min. heated to 170 ° C and then immersed in one of the nickel deposition baths described in Example A. A well adhering nickel film is formed on the coated resin surface.
• the epoxy polymer is a linear addition copolymer consisting of a diglycidyl ether based on bisphenol A (epoxy value: 5.3 Val / kg) and benzylamine in a molar ratio of 1: 1.
• the production follows the in J. Polym. Sci. Polym. Chem. Ed., 22 249 (1984).
• Example J 0.5 g of the complex according to Example 1, 0.5 g of the linear polyepoxide according to Example 1 and 10.0 g Makrolon® (cf. Example C) are dissolved in 70 g 1,2 dichloroethane. An epoxy resin plate is treated with the solution obtained as described in Example I. A well adhering nickel film is obtained on the coated resin surface.
• Example K 11.2 g (56.0% by weight) of a diglycidyl ether based on bisphenol A (epoxy value: 5.25-5.4 Vat / kg), 7.8 g (39.0% by weight) of hexahydropthalic anhydride and 1.0 g (5.0% by weight) of the complex according to Example 2 are mixed at 90 ° C. for 15 minutes. Then 0.06 g of benzyldimethylamine is added as an accelerator. After a further 5 minutes at 90 ° C., the mixture is poured into a mold preheated to 100 ° C. and cured for 4 hours at 100 ° C. and for a further 4 hours at 120 ° C.
• the molded body is tempered for a further 2 hours at 240 ° C. and then coated with nickel in a commercial nickel plating bath (Shipley Niposit® 468 or Niposit® PM 980). A well adhering nickel coating is obtained.
• the nickel plating can also be carried out using the nickel plating bath according to example A. Comparable results are achieved.
• Example L 22.4 g (50.8 wt.%) Of a diglycidyl ether based on bisphenol A (epoxy value: 5.25-5.4 val / kg), 15.4 g (34.9 wt.%) Hexahydrophthalic anhydride and 6. 3 g (14.3% by weight) of the complex according to Example 3 are mixed at 90 ° C. for 15 minutes. Then 0.1 g of benzyldimethylamine is added as an accelerator. After a further 5 minutes at 90 ° C., the mixture is poured into a mold preheated to 100 ° C. and cured for 4 hours at 100 ° C. and for a further 4 hours at 120 ° C.
• the molded body is annealed at 240 ° C. for 1 hour and then coated with nickel in a commercial nickel plating bath (Shipley Nisposit® 468 or Nisposit® PM 980). A well adhering nickel coating is obtained.
• the nickel plating can also be carried out with comparably good results using the nickel plating bath described in Example A.
• Example M 0.25 g tris (p, p'-diisopropyldibenzalacetone) palladium and 0.2 g polystyrene are dissolved in 20 ml toluene. This solution is used as a writing ink in a Hewlett-Packard "Thinkjet" printer with a modified writing head * ). With the printer, a text is written on a transparency for normal copiers (Folex® X-100). The film is then 15 min. annealed at 170 ° C. The film is then immersed in one of the nickel deposition baths written in Example A (duration 15 minutes). A nickel coating adheres well to the film at the printed areas.
• the ink reservoir is made of aluminum to increase resistance to organic solvents. In addition, all bonds are made with the solvent-resistant Araldit® adhesive.
• Example N 20 g of a photoresist from 120 parts by weight of a technical epoxy cresol novolak (epoxy content 4.5 equivalents / kg), 50 parts by weight a technical bisphenol A epoxy resin (epoxy content 0.5 eq./kg), 20 parts by weight Talc, 1 part by weight Irgatith green, 2 parts by weight ( ⁇ 6 -stylbene) ( ⁇ 5 -cyclopentadienyl) iron (II) hexafluorophosphate and 200 parts by weight Cyclohexanone is mixed with a solution of 0.5 g of the complex according to Example 2 in 15 ml of dichloroethane and mixed well.
• a technical epoxy cresol novolak epoxy content 4.5 equivalents / kg
• a technical bisphenol A epoxy resin epoxy content 0.5 eq./kg
• Talc 1 part by weight Irgatith green
• ⁇ 6 -stylbene ⁇ 5 -cyclopentadie
• This mixture is applied to a glass plate (200x100x4 mm) using a 70 ⁇ squeegee.
• the applied lacquer is dried for one hour at 80 ° C.
• the paint is exposed through a mask (5000 W Hg high-pressure lamp Berner M 061), 20 min. hardened at 135 ° C, and then developed by immersion in cyclohexanone for 1 1/2 min.
• annealing is carried out at 230 ° C in a forced air oven for one hour.
• the plate is then nickel-plated in a metallizing bath described in Example A. A well adhering nickel coating is created on the structured surface of the photoresist.
• Example 0 The procedure is as in Example N. Instead of a glass plate, an epoxy carbon fiber laminate is used as the substrate. After the irradiation, 10 min. hardened at 135 ° C. After development and metallization, a well-adhering nickel coating is created on the structured surface of the photoresist.

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• 1987
  • 1987-01-26 DE DE8787810046T patent/DE3760813D1/de not_active Expired
  • 1987-01-26 EP EP87810046A patent/EP0233145B1/fr not_active Expired
  • 1987-01-29 PH PH34785A patent/PH23902A/en unknown
  • 1987-01-30 JP JP62020351A patent/JPS62192584A/ja active Pending
• 1989
  • 1989-03-03 US US07/319,884 patent/US5045436A/en not_active Expired - Fee Related

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