DK143571B - METHOD OF DEPOSITION OF METAL - Google Patents

Description

(19) DENMARK

W (12) PUBLICATION <n> 11 + 3571 B

DIRECTORATE OF THE PATENT-OQ TRADEMARK

(21) Application No. 6041/70 (51) | m.CI.3 0 23 C 3/02 (22) Filing date 26 Nov. 1970 (24) Race day Nov 26 1970 (41) Aim. available May 27, 1971 (44) Presented 7. s ep. 1981 (86) International Application No. - (86) International Filing Day - (85) Continuation Day - (62) Master Application No. -

(30) Priority 26 Nov. 1969, 57862/69, GB May 26, 1970, 25205/70, GB

(71) Applicant MPERIAL CHEMICAL INDUSTRIES LIMITED, London S.W.1., GB.

(72) Inventor Timothy Douglas Andrews, GB.

(74) Associate Company Chas. Hude.

(54) Method of precipitating metal.

The invention relates to a method for precipitating metal into or onto a substrate by contacting the substrate with a powerless plating solution.

The deposition of metal on a substrate by powerless plating is not new and has been described e.g. in the U.S. Patent Specification No. 3,033,703 and Swedish Publication No. 304,662. The present invention

GQ

The compound utilizes a particularly useful group of organic compounds T * '' as deposition centers, providing a particularly advantageous photo-reproducible radical cation-reducing form with significant oxidative stability, which enables the production of stable image deposits.

The process of the invention is characterized in that in or on the substrate there is an active component formed by at least partial reduction of a salt of the formula:

'Jof- (CH = CH, n 7 ^ X

Λ N R R

- Ill —1

R

or 3 8

R R

"ΐΛ / '4 Vv * 9 T 04- (CH = CH) n -01 2x rJA ^ A r *" sA ^ A. "] l2 R11 wherein R1-r1 ° represents hydrogen, halogen or hydrocarbon groups, one or more of the groups may be linked to others on the same ring or neighboring heterocyclic rings, R and R represent hydrogen, hydrocarbon or substituted hydrocarbon groups, n is 0 or an integer, and X is an anion.

The term "powerless plating solution" is used in its usual sense in electroplating technology, i.e. a solution containing a metal salt and a reducing agent capable of precipitating metal without exerting an external electrical potential. The present invention consists in the discovery that, after reduction, the above-described organic compounds are capable of causing metal to precipitate from the powerless plating solution.

Once a metal trace has been precipitated on the organic material, the thus precipitated metal is capable of catalyzing further precipitation of the same metal or another metal from the appropriate solution and a metal layer can be built up.

The substrate containing or consisting of the 3 1 * 3571 organic compounds of claim 1 may optionally be first contacted with a sensitizer which comprises a solution of a compound of a metal from the plate group (Hu, Rh, Pd, Os, Ir, Pt), silver or gold, and then with the powerless plating solution. This technique is preferred in some cases where powerless plating without the sensitivities requires too long processing time or too high a temperature to be appropriate.

The substrate

The active component of the substrate is formed by reducing the compounds of claim 1. The active component may itself constitute the substrate, or a carrier may be used to carry the active component on or in itself. The carrier may be inactive to the active component or may have a stabilizing effect thereon. In this way, some usually extremely active radicals can be stabilized to allow treatment with the powerless plating solution, although there is a delay between their formation and reaction with the plating solution.

Preferred radical catalysts which may be used are those containing two unsaturated heterocyclic or azulene ring systems (both of which may be substituted) bonded directly or by a chain of conjugated unsaturation. Examples of such radical cations are tetrathiotetracene, tetraselentetracene, bis- (indolizinum) -ethylene, bis- (benzthiazolinylidene) -azine, bis- (quinolyl) -azine and bis- (azulenyl) -ethylene and substituted derivatives thereof, especially with lower alkyl (1-10 carbon atoms) and aryl, e.g. phenyl residues. These radical cations are used in the form of salts of anions such as halide, perchlorate, tetrafluoroborate, methylsulfate, bisulfate, acetate and polymeric anions such as poly (p-viylnylbenzenesulfonate), poly (acrylate) and poly (styrylphosphonate).

Another group of radical cations is that which, by reduction, is derived from the group of dications on which the aforementioned definition of active neutral compounds is based. This relationship will become clearer by using the following equation. Compounds such as bipyridyls can be oxidized / reduced according to the scheme: + + Λ ,, e. * Ez fc -----------------> z +, ......... ...--> z -e -e

Thus, a dication (the normally stable oxidation state in aqueous media), delivered with a single electron, forms a radical cation which * 43571 4 with an additional electron is converted to the neutral compound. Both Z + * and Z are active in the required manner in accordance with the invention with electrolysis-free plating solutions, where Z + is the stable form in aqueous media.

As mentioned, in the context of the present invention, neutral compounds and radical cations derived from dictations of the general formula (1) are used.

R3 R8 i * 9

Yl · - * ch, ^ OL (i> r1 IT R ^ R6 N R10 11 R1 ^ jjll 1-12 where R has the meanings given above.

The bond usually links the two aromatic rings in the 4,4 'or 2,2' position when replacing R3'8 or R5'6, e.g. 2,2'-bipyridyls and 4,4'-bipyridyls.

Substituent pairs on the same ring or neighboring rings can be bonds that form cyclic structures. X compounds containing a +, V-bipyridyl structure (2) h1 \ / r2 h9 \ / 10 B12 "R11 ^ 2 'B? Ή * b7 r6 may be pairs of R groups, e.g. , that a 12 h.

single divalent unsaturated organic group, especially the pairs R 5, R '·, jj9j10, r2.9 0g ^ 7. x (Xe. In the first four of these cases, the divalent organic group can form a fused aromatic ring, such as 2 Q Ll7 as in biquinolyl compounds. When both R '7 and R' 1 are bonded by ethylenic groups, a diazapyrene nucleus is formed.

win Ό

The active compound may be a simple compound or radical cation, or it may be part of a more complex molecule, as in di. It may also be polymer, in which case the active moiety may form in the polymer backbone in end groups or in side chains or in combinations of such positions.

The defined neutral compounds and radical cations described above and which will be described in more detail in the following Examples have the common feature that they can be formed by a cationic compound under the influence of heat or radiation. Salts containing monocations are reduced to neutral radicals.

Examples of monomeric cations having the above properties are (3) - (8).

((O) ^ ^ b-bipyridylium (P) (3) -o-O IJ + - H-V biquinolinium (¾) (f f)

o B

- + δ> CH = 1β-bis-1β-pyridyl) -ethylene (E) (5) Λ "0> -Λ - + N ()) - / () N + - 2,7-diazapyrinium (A) ( 6) 2,2'-bipyridyl (B) (7) I + | + ........ (^^ + - + + - (V-pyridyl) -pyridine lumen (M)

The reference letter, listed after each name, will be used in the following description to indicate the appropriate cation unit to avoid repeating the entire structural formula. CH 2 -P-CH 2, 2 Cl 1 thus represents N, Ν '-dimethyl-1 · -1, V-bipyridylium chloride. It is understood that in this nomenclature the CH 2 groups are bound to the nitrogen. However, it is to be understood that substitution on the carbon nanotubes in the core unit is possible. Such substituents include alkyl, aryl, aralkyl, alkaryl and oxyhydrocarbyl groups. Among the halogens, chlorine and fluorine are preferred. It is desirable that there be no groups which are easily reduced, e.g. Nog. Thus, when the symbols P, D, Q etc. are used, it is clear that as well as the parent compound, appropriately substituted derivatives, e.g. 2,2'-bipyric = dylium compounds.

The active component can be formed into or incorporated into the substrate in various ways. A solution of the active component can be used to impregnate a porous substrate such as paper, clothing, wood or plastic foam. A solvent suitable for the active component is used, e.g. organic solvents for neutral radicals and neutral compounds, aqueous or organic solvents for cationic compounds. For many applications, it is advantageous to prepare the substrate in the form of a film. This can be easily accomplished by solution casting, preferably in the presence of a polymeric support. In the case of the radical cations and neutral compounds prepared from the defined dications, the preferred method is to support the dicationic compound in a water-soluble or swellable film-forming polymer matrix and to convert the dicationic unit to radical cation or neutral compound in situ by radiation or heat . The process for making such films is described in detail regarding bipyridyl and related compounds in British Patent Specification No. 1,310,812.

For the monomeric cations previously mentioned as P, Q, E, A, B, M, ultraviolet radiation and electron beams are the preferred forms of radiation for conversion to the radical cation, and for longer exposure to the neutral compound.

Water-soluble or a swellable polymer suitable as the matrix material includes polyvinyl alcohol, polyammonium methacrylate, gelatin, alginates and maleic anhydride copolymers, e.g. with styrene-vinyl ether or ethylene.

7 U3 & 7 1

Suitable polysaccharides such as polysucrose may also be used. Poly = vinylpyrrolidone is also suitable and good results have been obtained with mixtures of film-forming polymers, especially with mixtures of polyvinyl alcohol with polyvinylpyrrolidone using 40-80% of the latter.

The amounts of salt and film-forming polymer used are not very critical as they are mainly dictated by practical considerations and required sensitivity. A film casting solution typically consists of water-soluble polymer 5-20 parts, salt-giving radiation sensitivity, whether simple or polymeric, 0.1-10 parts and water up to 100 parts. All parts are parts by weight. Of course, storage and processing must take place where there is no radiation of the kind to which the materials are sensitive.

Although water-soluble polymers are preferred, certain water-insoluble polymers can be used if dissolved in a suitable solvent. An example is a copolymer of 1,6-diaminotrimethylhexanes and terephthalic acid, which can be cast into films using a polar solvent such as dimethylformamide and a suitable salt.

Examples of compounds containing dications which can at least be converted to radical cations by heat or irradiation in the presence of a water-soluble or swellable polymer are: R - P - R 2X-, where R is: (9) -CH 3, X = Cl, Br, SiF6, HSO2 -, CH2 SO2 - (10) -CH2-CH2- <gN, X = Cl (21) -CHgCHgOH X = Cl (11) -CH CH .- (0 \ X = Cl. I -prop d (22) - (CH2) nC0N ^ X = Cl (12) X = Cl i -prop OCH3 CH3 (23) -CHgCO NH - ^ - OCH3 X = Cl (13) - ch0coJq \ x = ci * V- / (2V) -CH.C00C "Hk X = Br CH '225 (25) - ^ 0) -CN X = Cl (W-CH2 ^> (26) - <0> o ch3 8 t * SS71 U5) X = C1 (27) - ^) - 01 (16) -CELC0 NCC ^) «X = Cl / - \ 2 252 (28) - <g) -OC2H5 X = Cl (17) -CH. - / O) X = Cl / -v 2 \ / / (29) - (g) X = 01 (18) -CHpCo m- (o) x = ci ^ t-but = tertiary butyl (19) -CH2CO NH -t-but X = Cl i-prop = isopropyl (20) - (CH 2) CO CH 3 X = Br The groups R may be different as in

(30) ch3-p <g) -CR

M-R 'X "where R' is (3D - (g) -MCOCH? X = Cl (32) - <g) -0C2H5 X = Cl (33) - ch3 X = Cl

Other compounds tested are (3 ^) ch3-q-ch3 (CH3 SO0f) 055 <^> - A- <g) (bf, -) 2 (36) CH3-E-CH3 (CH ^ O ^^ CH2 (37) bC ^ | (Ci ") 2 ^ ch2 9 U9B71

The colors of the radical cations are generally green or blue or purple, but other colors can be obtained, thus compound C3 ^ -) gives a pink color.

(38) CH2 "P" k01 ~ (39) CH3 - P - ^ 201 "CIL - P - CfL / -v CH5 - P - CH, (M>) Compare CH3 - P - - P - CH3

CN CN

V1o (b-l) 8C1 "P - CH" Cft, - beer beer

CN CN

ZPCH2 n ^ v ° V2 ZPCH2vv / \ v CH2PZ

(^ 2) | (ST KM lk C1 'before - ch' - p - ch 'J \ yl ZPCH2 ^ \ / ^^^ ch2pz where Z is - CN or -CH ^

P

N N, _ (, 3) ΛΛ

Y T

wherein Y is a base such as pyridine, quinoline or a monoquaternized blpyrldyl (M).

10 ttwi

CH0 CEL

3 \ _ / 3 (W - ch2 - n ^ V- CH2 - P--) - (2C1- CEL 'CH-, o J n (W --CH2 - / OV ch2 - a--' - 2C1 ~ n 'γγ.

H N

(* t6) 3C1 "

ISLAND

Polymeric anions can also be used.

Zwitterion compounds are also effective, e.g.

- 00C. ^ C00 '(^ 7) ^ γΗ0 - P - CH ^ h3c ^^ ch3 n 143571

Streamless plating solutions are extensively described in the literature, especially the plating solutions for the precipitation of silver, copper and nickel. A general literature reference which contains useful formulas is W. G-oldie - "Metal Coating of Plastics", Vol. 1 (I968). Other useful. formulas can be found in the disclosure of Dutch Patent Application No. 69OI919 and the disclosure of German Patent Application No. 199983. Commercial solutions such as the "Enplate" series are suitable.

The most readily available solutions for use in the present invention are those containing Group VIU and IB metals together with mercury, lead, tin, antimony and bismuth.

Silver and copper-containing solutions in which the reducing agent is an aldehyde such as formaldehyde can be used. Silver containing solutions wherein the reducing agent is an aminophenol or one or more of the other common organic reducing agents used in photographic developers are also of general utility. A suitable iron, cobalt or nickel precipitation system comprises a hypo = phosphite solution. The preparation of specific solutions will be described in the Examples.

It is known that palladium and, to a lesser extent, other platinum metals, silver and gold, catalyze the decomposition of Beamless plating solutions. This phenomenon can be used in the present invention in sensitizing the active substrate by contacting it with a compound of the required metal, conveniently in solution, and then contacting this sensitized substrate with the powerless plating solution. A simple palladium salt can be used. Palladium chloride is particularly suitable at a concentration in the range of 0.001-10 parts per ml. 1000 parts of water. Platinum, other platinum metals, silver or gold salts can also be used. The preferred concentration of the platinum or palladium solution is approx. 0.1 parts per 1000 parts of water, based on the weight of the halide. The active substrate is typically immersed in the sensitizing solution for 0.5-5 minutes at 15-30 ° C, washed and then transferred to the powerless plating solution.

12 * 43571

The active, possibly sensitized substrate is contacted with the electroless plating solution until the required amount of metal has been precipitated. "This can usually be determined visually: the color of the organic compound disappears and is replaced by a finely divided metal which produces a dark image. The metallized image becomes darker when the first formed metal catalyzes the reduction of the solution. In this way, the optical close-up of the image can be identified.

Where the active components are contained in a film carrier based on a water-soluble or swellable polymer such as polyvinyl alcohol, certain precautions are necessary to prevent damage to or loss of the substrate during processing. If the substrate is contacted with the plating solution in cold solutions (e.g. room temperature), the water-soluble polymer should be chosen such that its solubility in cold aqueous media is far inferior to that of hot aqueous media. A suitable polyvinyl alcohol grade is a high molecular weight 99-100% hydrolyzed polyvinyl alcohol, e.g.

"Elvanol" grades 71-30, 72-60 or 73-12 ?, or "Gohsenol", all "N" grades. As an alternative or further precaution, the metal imaging process can be carried out in the presence of a high concentration of ions by the addition of inactive salts. 1-30% by weight of alkali metal or ammonium salts can be used: ammonium, sodium or potassium sulphates are preferred at concentrations of 1- % by weight of the plating solutions „

A further alternative or additional precaution is to pretreat a polyvinyl alcohol film with an aqueous borax solution or glyoxal solution to form the cross-links between polymer chain borax can be included in the plating solution.

It is also advantageous to include a surfactant in the plating solution. This reduces the tendency for premature metal precipitation. Long-chain amines can be used. For the same purpose can be used until? %, preferably approx. 2% by weight poly = vinylpyrrolidone.

When using a silver plating solution, some precautions are necessary to prevent the precipitation of silver halides. Either a halide-free substrate or a suitable complexing agent is used, and the use of polyvinylpyrrolidone in the above concentration gives this added benefit.

If powerless plating is continued for a sufficient period, sufficient metal is precipitated to conduct the substrate.

The precipitated conductive metal can then be further metallized by conventional electrolytic plating with the same or other metal. Plastic foam can also be made conductive using a similar technique.

Data capture applications.

An important application of the present invention is to render images permanent or intensified images (latent or visible) in the silver-free photographic systems, where the image is in the form of organic neutral free radicals, radical cations or defined neutral compounds. An example of such a system is described in British Patent Specification No. 1,310,812 and is based on nitrogenous salts which, upon irradiation, form radical cations. Preferred salts are those based on compounds containing two quaternized nitrogen atoms with a chain of conjugated unsaturation sites between the nitrogen atoms.

All of the previously described photosensitive compounds are useful in the context of this invention. The photosensitive compound is carried in a water-soluble or swellable film-forming polymer and converted by radiation, in particular ultraviolet or short-wave visible radiation, into essentially radical cations. The polymeric support material is capable of stabilizing the radical cations formed, but eventually the combined effect of oxygen and moisture blurs the image, unless kept in the desiccator or under similar dry conditions. If the radiative image is processed in accordance with the present method, it is rendered as durable as in conventional photographic systems, while retaining most of the high-resolution advantages of the photosensitive material, as already described. 1500 line pairs per resolution can be resolved. ran. However, care must be taken not to go too far with the metallizing process if the only aim is high resolution, as the growing area of metal precipitation will reduce the solution. Thus, in some cases, it may be necessary to adjust optical density resolution.

The film-forming polymer may contain, in addition to the active component, the additives described in British Patent No. 1310812 for (1) rate increase (i.e., compounds containing active hydrogen, as in alcohols and amines, including alcohols, phenols, carboxylic acids and sugars, e.g. glucose , oxalic acid, p-chlorobenzoic acids, glycerol, pheolene, ethylenediaminetetraacetic acid (disodium salt), picric acid, glycine, β-alanine, intermediate acid, triethanolamine, thiazine and nicotinamide adrenosine = dinucleotide phosphate)} (2) free base riboflavin in the visible region of the spectrum, acronol yellow (a dye comprising 3,6-dimethyl-2- (4-dimethylaminophenyl) benzthiazolium chloride) and alkaline solutions of the wood resin derivative known as collophonium , is capable of extending the sensitivity up to or above 50 ° nm and other sensitizers comprising 3'3'-diethylthiacyanide iodide, proflavin, acridino range, acriflavine, N-methylphenazinium methylsulfate, 4-cyanoquinolinium methiodide and erythrosine), (3) desensitizers, (i.e. compounds which can be added to decrease the spectral reactivity so that the film can be processed in daylight) include p-aminobenzoic acid, 6-amino-3,4-phthaloylacridone and urazole, (4) various additives (i.e. For example, ammonium chloride improves photosensitivity and film flexibility, and other water-soluble plasticizers such as urea, glycerol and other polyols may also be used to enhance this property. The sensitivity to X-rays can be increased by introducing a high atomic weight metal compound such as barium chloride).

Self-supporting films can be made from water-soluble polymers, conveniently having a thickness of 0.2 - 2 mm. However, the film is preferably made as a coating on a flexible support such as polyethylene terephthalate film, in which case the thickness of the coating can be reduced to 0.001-0.1 mm.

15

Data can be recorded on the film by ultraviolet or visible radiation of a suitable wavelength by electron beams or by infrared radiation which causes the film to be locally heated to a temperature at which the radical cation is formed. The exposed film should then be treated in accordance with the invention as soon as possible. If it is suggested to store the exposed film for a long time before treatment, it is desirable to do so under dry and oxygen = free conditions.

Other uses.

The fact that if electricityless plating is continued for a sufficiently long time an electrically conductive product can be greatly utilized. This may then be further plated by ordinary electrolytic plating. Thus, any article can be made conductive, provided that the appropriate activating component can be introduced thereon or therein by coating, aspirating, spraying, impregnating or other application method. The activating component may, of course, be derived from compounds of bipyridyl and related types, as discussed above. After insertion or formation of the activating component, the article is placed in the electroless plating bath until the desired metal amount is precipitated, optionally with a prior sensitization step.

Metallized foams can be made by taking a plastic foam, introducing the active component, plating without power, consolidating the precipitated metal by electrolytic plating, and possibly removing the plastic material by dissolution, firing or otherwise.

In another application, a circuit for the construction of electrical or electronic equipment is produced by forming a circuit-like distribution of activating component over a carrier, e.g. plastic laminate sheets, electrically plating (possibly after sensitization), and building the metal layer to a sufficient thickness by additional powerless or conventional electrolytic plating technique. It should be noted that no etching step is required. Also, due to the high resolution capability of the film, a high component density is possible.

f «5571 16

Circuits with regions of differential specific resistance can also be made using different metals in different parts thereof. An initial circuit-like distribution of active component is plated with a highly conductive metal, e.g. copper. Spacers are left open where lower specific conductivity is required and a second circuit-like distribution of active component is applied to connect the gaps. Then plaster to the required degree with a metal of higher specific resistance, e.g. mixtures of nickel and iron. This technique is applicable where a substrate is used in which the active component is bound in a polymer, e.g. polymers containing bipyridyl radical cations in the skeleton or side chain. For example, a film containing a bipyridyl salt is exposed. for ultraviolet radiation to form a first orbital image of radical cations, and this is electrically plated with a first plating solution, e.g. copper. Spaces are left open in the circuit where a resistance component is required. Since the bipyridyl salt, which is not converted to radical cation, is bound in the substrate, it can then be further subjected to ultraviolet radiation to form a second image of radical cations bound to the first. This is then plated with another plating solution 3 e.g. a mixture of iron and nickel to form resistance elements. The operation can be repeated with different metals if desired, but the metal with the lowest specific resistance should be precipitated first.

Typical methods of the invention are illustrated in the following examples wherein the parts are parts by weight.

Example 1.

A polyvinyl alcohol film containing 10% by weight of N, N * dimethylbi = pyridylium dichloride was illuminated with ultraviolet light through a negative of varying optical density. The resulting image was dark blue with an optical density in the range 0.1-1.5. This film was treated by immersing in a powerless plating solution for 20 minutes at 20 ° C. The developer was made on the basis of the following components dissolved in water and filled up to 1000 parts.

«3571 17

Anhydrous sodium sulfite 20 parts

Sodium thiosulfate pentahydrate 30 parts Silver nitrate 30 parts 2,2 - diaminophenol dihydrochloride 1.5 parts

Anhydrous sodium carbonate 1.2 parts

Anhydrous sodium sulfate! +0 parts

Sodium tetraborate parts

The first four components are based on a physical developer, published by A.F. Odell (J. Ind. Eng. Chem. 877 (1933). The last two components were added to reduce the effect of water on the polyvinyl alcohol film).

The blue color was removed and replaced with a dark brown image with an optical density in the range of 0.1-2.2 after washing and drying.

Similar results were obtained by replacing the sodium sulphate with potassium sulphate (-0 -0 parts) or ammonium sulphate (60 parts).

The 2,3-diaminodiphenol dihydrochloride was replaced by the same weight amount of p-methylaminophenol sulfate ("metol"), p-hydroxyphenylaminoacetic acid ("glycine") or p-aminophenol and good results were obtained.

Higher contrast and optical density can be achieved by reducing the amount of sodium = thiosulfate and increasing the pH by adding ammonia solution or sodium carbonate. It is necessary that this solution be stabilized against silver precipitation by the addition of a cationic surfactant (e.g., "Army 12"), and to prevent the precipitation of the cationic agent, it is also necessary to add a nonionic agent (e.g. e.g., "Lissapol N"). An appropriate amount of detergent is 0.001-0.1% by weight.

Example 2.

This developing solution gives a higher optical density but is unsuitable for film materials containing halides due to the silver halide precipitating. The developer was prepared by dissolving the following components in water and diluting to 1 liter.

18 t «SS? 1

Citric acid 20 parts Silver nitrate Ij7? parts p-methylaminophenol sulfate 0 parts "Lissapol Nu> | 0.2 parts> surfactants" Army 12 "J 0.2 parts

Anhydrous sodium sulfate ifO parts

A polyvinyl alcohol film containing 10% by weight of N, N'-dimethylbi = pyridylinmethylsulphate was illuminated with ultraviolet light through a wire mesh to obtain the optical density obtained was approx. 2. After immersing in the above solution for 10 minutes at 20 ° C, washing and drying, the silver image had an optical density of more than the exposed areas.

Example λ.

The procedure described in Example 2 was repeated, but the surfactants were replaced with polyvinylpyrrolidone (20 parts).

With this solution it became possible to use active components without halides without unacceptable obscurity.

Example

A glass plate coated with gelatin was immersed in a 10% aqueous solution of N, N-dimethylbipyridylium dichlorido. The plate was dried and illuminated with ultraviolet light through a metal mesh.

After exposure, the plate was immersed in a solution containing

Copper sulfate pentahydrate 10 parts

Sodium hydroxide 10 parts

Sodium tartrate 50 parts diluted to 1000 parts, to which were added 10 parts 37 ° formaldehyde = solution. The blue image turned dark brown. After washing and drying, the density was greater than 2.

Example H.

19 1 «3 $ 71

A glass plate coated with gelatin (25 µm thick) was immersed in a solution of N, N, -dimethylbis- (pyridinium) methylsulfate (10% aqueous solution) for 1 minute, rinsed with distilled water for J seconds and then allowed allowed to dry. After exposure in ea. ? Minutes through a line negative with a 100 watt mercury vapor lamp at 100 cm, the plate was immersed in a palladium chloride solution made of PdClr, (0.1 parts), concentrated hydrochloric acid 10 parts and water (to 1000 parts). After 1 minute, the plate was removed, washed with water and developed in a nickel-based powerless plating solution made from

Nickel dichloride (6 ^ 0) 2j parts Malic acid (monosodium salt) 6J parts

Gluconic acid (sodium salt) JJ parts

Ammonia (solution density 0.880) to pH 9

Sodium hypophosphite 35 parts

A strong black image was obtained after 1 minute and the optical density in fully illuminated areas was greater than 3.

The procedure described above was repeated using successively as a sensitizer 0.1 part PtCl 2 and AuCl 2 with hydrochloric acid (10 parts) and then AgNO 2 (0.1 part) with nitric acid (10 parts).

Similar sensitization was noted.

Example 6

The procedure of Example J was repeated using the palladium sensitizer, but the residence time in the nickel solution was increased to 30 minutes. The image had a metallic appearance and was sufficiently conductive to be plated electrolytically.

Example 7

A polyethylene terephthalate film ("Melinex") pre-coated with an alkyd resin varnish was coated with a solution containing 20 parts of poly (N-poly (p , 0 parts

Ammonium chloride 0.2 parts

Water to 150 parts

The solution was evaporated to form a sensitive coating of approx. 0.025 mm. The treatment was performed under subdued artificial light. The film was exposed through a line negative for 3 minutes under the conditions described in Example 5. After exposure, the film was immersed in a solution of aurichloride (0.5 parts) and concentrated hydrochloric acid (10 parts) in water (to 1000 parts) for 1 minute.

After washing, the development was carried out by immersing in a commercially available, nickel-pitting, nickel-pitting solution "Enplate Ni-410" at room temperature for 5 minutes. A black image was obtained with an optical density in the fully exposed areas larger than 2.

Example 8.

Two pieces of coated film, prepared as in Example 7, were exposed and sensitized with a palladium salt as in Example 5. They were then washed and developed in the following solution.

'Cobalt Trichloride (βΗ ^ Ο) 27 parts

Sodium citrate (20%) 90 parts

Ammonium chloride parts

Sodium hypophosphite 7.5 parts

Water to 1000 parts pH with ammonia solution set to 8.5.

You got a brown picture.

One piece was subjected to prolonged development (* + 5 minutes) and the other to a higher dissolution temperature (~ 80 ° C, 3 minutes). In both cases, conductive cobalt films were obtained.

Example 9

21 f * 3C91

A glass plate was coated, exposed and sensitized by the procedure described in Example 5. After washing, the gelatin layer was hardened by formaldehyde treatment (5 minutes) in a solution consisting of

Formaldehyde solution (* f0%) 10 parts

Sodium carbonate (anhydrous) 5 parts

Water to 1000 parts

It was developed in the following solution for 3 minutes at 80 ° C.

Cobalt chloride (6H2O) 60 parts

Nickel chloride (6 ^ 0) 2 parts

Sodium potassium tartrate (ten oz) 200 parts

Ammonium chloride 50 parts

Sodium hypophosphite 17 parts

Water to 1000 parts

Ammonia to pH 9 ·

You got a dense black picture.

Example 10.

A plate was coated, exposed and sensitized as in Example 5 and then developed for 10 minutes at room temperature in the following solution.

Ferrosulfate (7H2O) 120 parts

Sodium citrate (2H, 10) 70 parts EDTA 50 parts

Sodium hypophosphite 85 parts 38% formaldehyde solution 200 parts

Water to 800 parts

Ammonium hydroxide solution to pH 10.

You got a dense black picture.

Example 11.

22 f «8sn

A solution of diphenylpicrylhydrazyl (2% in acetone) was used to draw a picture on a piece of a polyvinyl alcohol film which was then dried under nitrogen. The film was sensitized with 0.1% palladium chloride solution and then developed in the copper plating solution of Example. After 5 minutes, the image had a dark brown-black appearance. After 30 minutes, the image was metallic and had a specific resistance of approx. 200 ohm / area hsd.

Example 12.

An open cell polyurethane foam was impregnated with a solution containing

Poly vinyl alcohol 20 parts

WjN'-dimethylbipyridylium methylsulfate 1 part

Water to 1000 parts

The foam was freed from excess liquid, dried and the radical formed by heating to 100 ° C for 30 minutes. .

Example 13

The surface of a piece of phenolic formaldehyde laminate was roughened (by sanding with scrap paper), coated with the following solution and then allowed to dry ', 23 * 49571

Polyvinyl Alcohol ("Elvanol 100-30") 10 parts (cross-linking middle Glyoxalhydrate 1 part)

Paraquatichloride 0, | parts

0.2 ml

Water to 100 parts

After ultraviolet light illumination through a printed circuit negative, the plate was developed in the following solution for 30 minutes at room temperature (20 ° C).

Copper sulfate pentahydrate CuSO ^ j ^ H ^ O 10 parts

Sodium potassium tartrate!? 0 parts

Sodium hydroxide 10 parts 37% formaldehyde solution 10 parts

Water to 1000 parts

The resulting copper precipitate had a specific resistance of less than 1 ohm / area unit and the thickness could be built up by electrolytic plating or continued immersion in the above solution. These thicker copper bottom faids (25 - 50 μ) could be reconciled in the usual manner.

Example 1 * f.

A polyethylene terephthalate film ("Melinex") with a coating of an alkyd resin varnish was coated with a solution containing N, N * -p-cyanophenyl-1 +) -lf-bipyridylium dimethyl sulfate 1.0 part

Polyvinyl alcohol, high molecular weight, high degree of hydrolysis 10 parts H₂O ^ to pH 3-k

Water to 100 parts

The solution was evaporated at a temperature of not more than 7 ° C, giving a sensitive coating of approx. 0.003 mm.

24

The treatment was performed under subdued artificial light. The film was exposed to electrons from a scanning electron microscope. Electron = energy was varied from 10-80 keV. Specific spot size was 0.2-0.5 µ »The color of the image was dark green. After developing in the plating solution of Example 1 for 5 minutes, the exposed film showed regular line patterns. 2000 line pairs per mm was dissolved very well.

Upon extended exposure with electrons, the image turned red due to the formation of the neutral compound, which could also be plated with the solution of Example 1.

Example 15

A coated polyethylene terephthalate film was prepared as in Example 14 and illuminated with ultraviolet light in the cavity of an electron spin resonance spectrometer. The optical density reached 0.5 at 610 nm. The radiocalculation image was immersed in the plating solution of Example 1 and a very dark brown image with optical density greater than 4 was obtained.

Example 16.

A coated polyethylene terephthalate film was prepared as in Example 14 and exposed to electrons in a scanning electron microscope at an energy of 5 ° Kev. The exposed film had an optical density of 0.5 at 610 nm, and the radical concentration was 1.4 x 10 ° spin / cm, measured by electron spin resonance. After immersion in the plating solution of Example 1, the image was examined by electron microscopy and it was found to have dissolved more than 1500 line pairs / mm.

Example 17

A coated polyethylene terephthalate film was prepared as in Example 14 and illuminated with ultraviolet light through a metal mesh for Preparation 25, a dark green radical cation image. An electrolysis-free plating solution was prepared by the method described in Belgian Patent No. 637398;

Solution A

Ferroammonium sulfate 78 parts

Ferrin nitrate 8 parts

Citric acid 10.5 parts "Lissapol M" 0.2 parts

Dodecylamine 0.2 parts

Water to 1000 parts

Solution B

Silver nitrate 8.5 parts

Water to 100 parts Before use, 1 part B was mixed with 9 parts A. After 5 minutes immersion in this solution a black image was obtained.

Example 18.

An aqueous solution containing 3 parts of a polymer consisting of units of structure β - 2 - 2 HSO 4 - and 15 parts of polyvinyl alcohol was prepared.

A film formed by writing on a glass plate provided a blue or purple radical cation image by ultraviolet light illumination. The image was developed with the plating solution of Example 1 to give a black image.

Example 19.

A polymer was prepared from p-xylylene dichloride and 2,2'-bipyridyl. The polymer analysis corresponded to the repeating units:

Claims (2)

A polyvinyl alcohol filia containing this polymer quickly turned blue by exposure to sunlight, and by immersing in the plating solution of Example 1, a black precipitate product was obtained. Example 20. A film was cast from a solution containing 10% polyvinyl alcohol, 1% N, N'-bisphenyl-2,7-diazapyrinium difluoroborate, 0.2% ammonium chloride, 0.5% glucose The film reacted to light of a wavelength of up to at least * +36 nm to form a radical cation image which was blackened by immersion in the plating solution of Example 3. Example 21. A film was cast according to the procedure described in Example 20 using 1,2-bis- (1 '). -methyl-lf'-pyridinium) -ethylene-di- (methylsulfate) It provided a magenta image in sunlight when exposed through a metal mesh.The magenta image became black by immersion in the plating solution of Example 3. Patent Claim. A method of precipitating metal in or on a substrate by contacting the substrate with a powerless plating solution, characterized in that in or on the substrate there is an active component formed by at least partial reduction of a salt of the formula: f R8 H r4 r7 r9 In GI <ch = ch) n-fGi R1 R R6 / ls, NvAsR10 or R11