CS216153B2 - Method of activation of organic material - Google Patents

Abstract

1335962 Electroless plating active substrates IMPERIAL CHEMICAL INDUSTRIES Ltd 5 Nov 1970 [26 Nov 1969 26 May 1970] 57862/69 and 25203/70 Heading C7F [Also in Division G2] Metal is deposited electrolessly in or on a substrate containing or consisting of an organic compound selected from (1) radical cations Z<SP>+</SP> or (2) neutral molecules Z derived by twoelectron reduction from a dication unit which is a salt containing N atoms at least two of which are quaternised and are contained in linked at least partially aromatic rings, the link providing a chain of conjugated unsaturation between the N atoms, and said dicationic unit being Z<SP>+</SP> in the equation where Z<SP>++</SP> is the normally stable state of the molecule in aqueous media. The radical cation may contain two unsaturated heterocyclic ring systems linked by a direct link or an azine or ethylene group, e.g. bis (indolizinium) ethylene, bis (benzothiazolinylidene) azine, bis (quinolyl) azine, bis (azulenyl) ethylene, and derivatives thereof, e.g. with C 1-10 alkyl or aryl substituents Associated anions may be halide, ClO 4 <SP>-</SP>, BF 4 <SP>-</SP>, CH 3 SO 4 <SP>-</SP>, HSO<SP>-</SP> 4 acetate, and polymeric ions such as poly (p-vinylbenzene sulphonate), poly (acrylate) and poly (styrylphosphonate). Preferred neutral compounds and radical cations are derived from dications of formula where R<SP>1-12</SP> are H, halogen, organic substituents, and n = 0 or an integer; various R may link to form rings. Examples are 4, 4'-bipyridilium; 4, 4'-biquinolinium; 1, 2-bis (4-pyridyl) ethylene; 2, 7-diazapyrinium; 2, 2'-bipyridyl; or 4, (4'- pyridyl) pyridinium, and their derivatives. The active compounds may be impregnated into paper, cloth, wood, or plastics foam, in an organic solvent or in water for type (3) compounds. The substrate may also be produced in the form of a film for silver-free photographic systems, by supporting a dicationic compound in a watersoluble or film-forming polymer matrix, e.g. of polyvinyl alcohol, poly (ammonium methacrylate), gelatine, alginates, maleic anhydride copolymers, polysaccharides, or polyvinyl pyrrolidone, or a 1, 6, diaminotrimethyl hexane/terephthalic acid copolymer cast into a film using DMF as a solvent may be employed. In use the film is exposed to radiation (UV, IR, visible or electronbeam) so that exposed parts are activated imagewise and are susceptible of development by selective electroless plating. The film is preferably a 0À001-0À1 mm film on a flexible support such as polyethyleneterephthalate, and may include (1) compounds for speed improvement (alcohols, phenols, carboxylic acids, sugars, glycerol, EDTA Na 2 picric acid, #-alamine, mellitic acid, triethanolamine, thiazine, or nicotinamide adenosine dinucleotide phosphate) (2) sensitisers, (riboflavin, Acronol (RTM) yellow, colophony, 3, 3' diethylthiacyanide iodide, proflavin, acridine orange, acriflavin, N-methylphenazinium methyl sulphate, 4-cyanoquinolinium methiodide or erythrosin (3) desensitizing agents (p-aminobenzoic acid, 6-amino-3, 4-phthaloy (acridone or urazole) and (4) other additives such as NH 4 Cl, urea, glycerol, or polyols to improve film pliability, or BaCl 2 to improve X-ray sensitivity. Development of the film image, or metallisation of a substrate, is by (1) optionally, if desired, treatment, e.g. for 0À5-5 mins at 15-30‹C, in 0À001 to 10 parts per 1000 in water of a salt of Ru, Rh, Pd, Os, Ir, Pt, Ag or Au, and (2) immersion in an electroless bath to provide a coating or image of Ag, Cu, Ni, Co, Co/Ni, or Fe, suitable baths being disclosed. Where the polymer of the film is water soluble or swellable, electroless plating is at room temperature or 1-30% of an alkali metal or ammonium salt, e.g. sulphate, is added to the bath to reduce damage to the film, or else same is pretreated with aqueous borax or glyoxal to induce cross-linking. The plating solution desirably contains a surfactant. Metal foam may be made by introducing the active compounds above into plastics foam, electroless plating, electro-plating, and optionally dissolving or burning out the plastics, and printed circuits may be made by circuit wise distribution of active compound followed by electroless plating, a 2- stage process using first Cu and then Fe-Ni for conductors and resistors in the circuit.

Description

The invention relates to a process for activating organic materials, in particular water-soluble or water-based materials. water swelling polymers before electroless plating.

Plating of organic materials is generally difficult and proceeds in a way that has not yet been sufficiently explained; some method of increasing the sensitivity of the metallized surface is necessary, for example by abrasion or initial application of a metal trace.

As used herein, the term &quot; electroless plating solution &quot; is normally used in electroplating technology and is a solution containing a metal salt and a reducing agent capable of depositing metal without introducing electrical current.

The invention is based on the finding that certain organic compounds have the ability to cause deposition of metal from electroless plating solutions. Once a trace of metal is deposited on the organic material, the deposited metal is able to catalyze further deposition of the same metal or metal. of different metals from the appropriate. solution and a metallization layer may be formed. Note ^(Atek that certain organic compounds have the ability to cause metal deposition on organic materials is new.

The substrate itself contains such an organic compound or consists of or stores such an organic compound. In some cases, the substrate is first contacted with a sensitivity enhancer comprising a solution of a platinum group metal compound (rubidium, rhenium, palladium, osmium, iridium, platinum), silver or gold, and then a current-free plating solution. This method is preferred when. simply electroless plating without increasing sensitivity is tedious and requires too high temperatures.

According to the invention, the activating component of the metallized substrate is the aforementioned organic compound. The activating component may itself form a substrate or a carrier may be used which contains the activating component or is carried by the activating component. The carrier can. be inert to the activating component, or may have a stabilizing effect on the activating component. Thus, the activator component can be stabilized such that treatment with the electroless plating solution is possible, even if there is a delay between the formation of the activator component and the reaction with the plating solution.

The invention therefore relates to a process for activating organic materials, in particular based on water-soluble or water-swellable polymers, prior to electroless plating, which comprises the step of: an activating substance derived from a cation of the general formula is deposited on the substrate

wherein R ^1-12 are hydrogen, halogen or an organic substituent, n 'is 0 or an integer.

A bond joins the two cores as a rule at the 4,4 'or 2', 2 'position when it replaces R ³ ' ⁸ or R ⁵ ' ^6, for example, 2,2'-bipyridyls and 4,4'-bipyridyls.

Pairs of substituents on the same ring or adjacent rings may be bonded to form cyclic structures. For example, in compounds of the structure 4,4 b-bipyridyl (2)

may be a pair of R groups are joined to form a single divalent unsaturated organic groups, especially ^with a pair of R, R ^{<5 9} R ^'10, R ^{6' 7,} R ² 'and R ^{4' 9 '7th} In the first four of these cases, the divalent organic group may form an aromatic nucleus as in the bichinolyl compound. If they are. R ^{2, Q} and R ^{4 '7} connected ethylene -carbonyl, thus creating diazapyrenové core.

The active compound may be a single compound or a radical, or the active compound may be part of a more complex molecule as in a dimer. It may also be polymeric, in which case the active unit may be contained in a polymeric backbone, end groups or side chains or a combination of these positions.

The defined neutral compounds and radical cations which have already been generally described and which will be described in more detail in the following examples have. the common feature that they are made of cationic

by exposure to heat or radiation. Salts containing monocations are reduced to neutral radicals.

An advantage of the process according to the invention is that it is possible to impart conductivity to any product of organic material when a suitable activating component according to the invention is introduced into or onto it, by coating, impregnating, spraying or otherwise suitable. After the introduction of such an activating component, the article is then placed in the electroless plating bath and left in the bath until the desired amount of metal is deposited on the article.

Examples of monomeric cations with the properties already described are given in the general formulas (3) to (8).

4,4‘-bipyridylium (P)

4,4‘-Bichinolinium (Q)

1,2-bis (4-pyridyl) ethylene (E)

2,7-diazapyrinium (A)

2,2‘-Bipyridyl - (B) (3) (4) (5) (6) (7)

4- (4‘-pyridyl) -pyridinium (M) (8)

The letters after the chemical names are used in the following description to denote a suitable cation so as not to repeat the entire structural formula. Therefore, CH3-P-CH3.2Cl represents -N ', N‘-dimethyl-4,4‘-bipyridylium chloride. It is included in this nomenclature that the -СНз groups are bonded to nitrogen. However, it is to be understood that substitution of carbon atoms on the nucleus is possible. Such substituents include alkyl, aryl, aralkyl, alkaryl and oxyhydrocarbyl groups. Of the halogens, chlorine and fluorine are preferred. It is desirable not to include readily reducible groups, such as NO 2. Therefore, when -D, Q, etc. are used, it is clear that appropriately substituted derivatives, for example 2,2‘-dimethyl-4,4‘-bipyridilium compounds, can also be used in addition to the parent compound.

The active ingredient may be formed in the substrate or may be applied to the substrate in various ways. The active ingredient solution can be used to impregnate porous carriers such as paper, fabric, wood or foamed plastic. Solvents suitable for the active ingredient are used, for example organic solvents for neutral radicals and neutral compounds, aqueous or organic solvents for cationic compounds. In many applications it is desirable to form a substrate in the form of a film. This is readily accomplished by solution in the solvent by casting in the presence of a polymeric carrier. In the case of radical cations and neutral compounds prepared from defined cations, a preferred embodiment is to support the dicationic compound with a water-soluble or swellable film-forming polymer matrix and to convert the dikationic units to a radicalkiller or a neutral compound in situ by irradiation or heating.

For the monomeric cations already mentioned by the letters - P, Q, E, A, B, M, ultraviolet irradiation and electron beams are preferred as suitable forms of irradiation to convert the radical cations to a neutral compound.

Water-soluble or water-swellable polymers suitable for matrices include polyvinyl alcohol, polyammonium methacrylate, gelatin, alginates, maleic anhydride copolymers, such as styrene-vinyl ether or s-ethylene.

Other polysaccharides such as polysaccharose may also be used. Polyvinylpyrrolidone is also suitable and good results have been obtained with a mixture of film-forming polymers, especially a mixture of 'polyvinyl alcohol with polyvinylpyrrolidone in use'. ^'40-80:% polyvinylpyrrolidone.

The proportions of the salt and of the film-forming polymer used are not particularly critical and are governed mainly by practical considerations and the desired sensitivity. A typical film casting solution consists of 5 to 20 parts water-soluble polymer ^; from 0.1 to 10 parts of the salt conferring irradiation sensitivity in both simple and polymeric state and from water to 100 parts. All 'parts' and amounts are always by weight. Storage and handling must, of course, eliminate radiation to which the material is sensitive.

Although water-soluble polymers are preferred, water-insoluble polymers can also be used if dissolved in a suitable solvent. An example is a copolymer of 1,6-diaminotrimethylhexane and terephthalic acid, which can be cast to form a film using a polymeric solvent such as dimethylformamide and a suitable salt.

Examples of 'dikation-containing' compounds that can be converted to at least radical cations by heat or irradiation in the presence of a water-soluble or water-swellable polymer are:

R - - P - R 2X - wherein R is Italy (9) —СНз, X = Cl, Br, SiFe, HSO4-, CH3SO4— (10) Italy (11) -c ^ c ^ -yo) (12) Octi, (13) -0 ° _ζ 00 ° & CH ^} (14) - _c ^ §) (15) (16) —CH 2 CO N (C 2 H 5) 2 (17) (18) -CH _from CO

(19) —CH2CO NH-t-but. X = Cl X = Cl Italy (20) - (CH 2) CO CH 3 X = Br X = Cl Italy (21) —CH2CH2OH X = Cl X = Cl Italy (22) i-prop  ' - (CH 2 d CCNI X = Cl

\ i-prop

X = Cl Italy (23) —CH2CO —o ) CHsX = X = Cl (24) —CH3COOC2H5 X = Br X = Cl Italy (25) -O-- ^cn X = 'Cl X = Cl Italy (26) X = Cl X = Cl Italy (27) X = Cl X = Cl (28) X = Cl - © X = Cl

(29) t-but = tertiary butyl i-prop as isopropyl

The R groups may be as in

M — R ‘Xwhere R‘ is [30] (31)

(33) —No X = Cl

Other compounds that have been tested are (34)

СНз — Q — CH 3 (CH 3 SO 4 -) 2 (35) (36)

СНз — E — CHa (CH3SO4-) ((37) in I (co ₂ ^ч сн ₂

The colors of the radical are mainly green or blue or magenta, but other colors may be obtained, for example, compound (34) gives a pink color.

(39)

CH _yy 2'Cl

C-P-CH-2-C1 (40)

CH-P-СС / _Х ГН.-Р-СН ₁

CHfP-CH, CH-P-CH ₃ ^{3 2} * 8 Cl

(42) wherein Z is

(43) cr wherein B is a base such as pyridine, monoquernized bipyridyl quinoline or (M).

(44)

CH-P-2СГ

CH _Z -A -

CT Jn

Polymeric anions may be used. Amphoteric compounds, for example (47) —ООО000 \ /

НС — P — CH / \

НзС СНз are also effective.

Electroless plating solutions are well described in the literature; Particularly well described are solutions for electroless plating with silver, copper and nickel.

The most suitable solutions for the process are those comprising Group VIII and Group IB metals together with mercury, lead, tin, antimony and bismuth.

Solutions containing silver and copper and formaldehyde as reducing aldehyde may also be used. In general, silver-containing solutions in which the reducing agent is aminophenol or one or more other conventional organic reducing agents used as photographic developers are also useful. A suitable plating system for iron, cobalt or nickel comprises a hypophosphite solution. The preparation of specific solutions will be described in the examples.

It is known that palladium and, to a lesser extent, other platinum group metals, silver and gold catalyze the decomposition of electroless plating solutions. This phenomenon is used in the method of the invention to increase the sensitivity of the active substrate by contacting the substrate with increased sensitivity with the metal compound in solution and then contacting the substrate with increased sensitivity with the electroless plating solution. Simple palladium salts can be used: very good, palladium chloride at a concentration of 0.001 to 10 parts per 1000 parts water is suitable. Similarly, salts of platinum, other platinum metals, silver or gold may be used. A concentration of platinum or palladium solutions of about 0.1 parts per 1000 parts of water, based on the mass of halide, is preferred. Most preferably, the active substrate is immersed in the activator solution for 0.5 to 5 minutes at a temperature of 15 to 30 ° C, rinsed and transferred, to the electroless plating solution.

The active substrate, or even the substrate with increased sensitivity, is contacted with the electroless plating solution for as long as the desired amount of metal is applied. This is usually judged visually: the color of the organic compound changes and is replaced by finely dispersed metal to produce a darker image. The metallized image darkens as soon as the precipitated metal first catalyzes solution reduction. In this way, the optical density of the image is intensified.

If the active ingredient is contained in a water-soluble or swellable polymer-based nasal film, such as polyvinyl alcohol, certain measures are necessary to prevent damage or loss of the substrate during processing. If the process of contacting the substrate with the plating solution is carried out cold, for example at room temperature, then the water-soluble polymer must be selected such that its solubility in the cold aqueous medium is much less than in the hot aqueous medium. A suitable type of polyvinyl alcohol is a medium to high molecular weight polyvinyl alcohol of from 99 to 100% by weight. Another additional or additional measure is to work in the presence of a high ion concentration by adding inactive salts. 1 to 30% by weight of alkali metal or ammonium salts may be used: ammonium, sodium or potassium sulphate in a concentration of 1 to 5% by weight, based on the plating solutions, is preferred.

Another alternative or additional measure is pretreatment of the polyvinyl alcohol film with an aqueous borax or glyoxal solution to crosslink the polymer chains; borax can be introduced into the plating solution.

It is also preferred to add a surfactant to the plating solution. Reduces the tendency to deposit metal too early. Long chain amines may be used. Up to 5%, preferably about 2% by weight of polyvinylpyrrolidone can also be used for the same purpose.

If a silver-based plating solution is used, some precautions are necessary to prevent the precipitation of silver halides. Either a halide-free substrate or a suitable complexing additive and optionally polyvinylpyrrolidone at the concentration just mentioned is used.

If electroless plating is carried out for a sufficiently long time, the substrate becomes conductive when a sufficient amount of metal is deposited. The conductive metal layer may then be further metallized by conventional electroplating by the same metal or other metal. Conductivity can also be imparted to plastic foams by this technique.

An important application of the method of the invention is to produce a permanent image or intensify the image of latent or apparent silver-free photographic systems, wherein the image is in the form of organic neutral free radicals, radical cations or defined neutral compounds. Preference is given to salts based on compounds containing quaternized nitrogen atoms with chain-conjugated double bonds of muscles with nitrogen atoms. All of the above-mentioned photosensitive compounds can be used in the process according to the invention. The photosensitive compound carried by the water-soluble or water-swellable polymer under irradiation with particularly ultraviolet or short-wave visible rays is converted predominantly to radicalcation ions. The polymeric carrier is able to stabilize the radicals formed, but the combined action of oxygen and moisture whites the image if not dried. When the radical cation image is processed by the method of the invention, it is stable as in a conventional photographic system and has numerous advantages for high resolution capability associated with the light-sensitive material already described. 1500 pairs of mm ^-1 lines were distinguished. However, care must be taken that the plating does not proceed so far that the increasing metal layer does not reduce the resolution. Therefore, in some cases, it is necessary to balance the resolution and optical density.

The film-forming polymer may contain, in addition to the active ingredient, speed enhancing agents, for example active hydrogen-containing compounds, such as in alcohols and amines including alcohols, phenols, carboxylic acids and sugars such as glucose, oxalic acid, p-chlorobenzoic, glycerin, phenol, ethylenediaminetetraacetic acid (disodium salt), picric acid, glycine, O-alanine, mellitic acid, triethanolamine, thiazine and nicotinamide, adenosine, dinucleotide, phosphate, (2) susceptibility enhancers, for example compounds enhancing resolution to the visible region spectra such as riboiflavHV as the free base, yellow-based 3,6-drmethyl-2- (4-dimethylaminophenyl) benzthiazolium chloride and alkaline solutions of wood-resin derivatives known as rosin, capable of extending the sensitivity up to or above 500 nm, and other sensitizing agents such as 3,3'-diethylthiocyanate iodide, proflavine, acridine Orange, acrifovine, N-methylphenazinium methylsulfate, 4-cyanoquinolinium methiodide and erythrosine, (3) sensitizing agents, such as substances that may be added to reduce sensitivity to light, so that the film can be handled daily light, including p-aminobenzoic acid, 6-amino-3,4-phthaloylacridone and urazole, (4) various additives. for example, compounds that can be incorporated into the film to modify light sensitivity or to modify the physical properties of the treated material. For example, ammonium chloride improves light sensitivity as well as film drapability; other water-soluble emollients such as urea, glycerin and other polyols may also be used to improve this property. X-ray sensitivity can be increased by introducing high atomic metal compounds such as barium chloride.

Self-supporting films can be prepared from water-soluble polymers; these films generally have a thickness of 0.2 to 2 mm. Preferably, however, the film is prepared as a coating of a flexible base and as a polyethylene terephthalene film if the thickness can be reduced to 0.001 to 0.1 mm.

Data can be recorded on the film - using ultraviolet or visible light of suitable wavelength, electron beam or infrared rays, which causes the film to be heated locally to a temperature at which a radical is formed. The exposed film is then processed by the process of the invention as soon as possible. If the exposed film needs to be stored for an extended period of time prior to processing, it is desirable to store the film in a dry environment and / or under oxygen depletion conditions.

An important field of application is based on the fact that, when electroless plating is carried out for a sufficient period of time, an electrically conductive product is obtained, which can then optionally be further metallized by conventional electroplating. Therefore, conductivity can be added to each article when a suitable activator component is introduced into it or by coating, impregnation, spraying or other suitable means. Moreover, the activator component can be derived from bipyridyl and related types of compounds, as mentioned above. After introduction or formation of the activating component, the article is introduced into a electroless plating bath and left in the bath until the desired amount of metal has deposited on the article, optionally with a sensitizing pretreatment.

The metallized foamed plastic is prepared by introducing an active ingredient into the plastic foam, the foam is then electrolessly plated, the deposited metal is then plated electrolytically and optionally dissolved, burned or otherwise removed by the plastic material.

In other cases, current for the construction of electrical or electronic devices is obtained by providing a current distribution of the activating component over the base substrate, for example by plastic lamination, electroless plating, after possible sensitization, and by forming a metal coating of sufficient thickness by another electroless or conventional -plated. It should be noted that no etching is needed. Also, due to the high resolution of the film, a high component density is possible. Streams can also be obtained between regions of different resistivity by using different metals at different locations. The first jet-active arrangement is deposited with a metal of high conductivity, for example copper. In places where a lower conductivity is observed, gaps are omitted and a second current arrangement of the active component is applied to fill the gaps. This is then metallized to the desired extent with a metal of greater resistivity, for example nickel-iron mixtures. This technique is useful where a substrate is used in which the active ingredient is bound in a polymer, i.e. bipyridil radical containing polymers in the main or side chain. For example, a film comprising a bipyridil salt is exposed to ultraviolet radiation to form a first stream image of radical cations and the assembly is electrolessly plated in a first plating solution, i.e., copper. Where a component of - greater resistivity is required, gaps are left. Since the bipyridil salt, which is not converted to a radical cation, is bound in the substrate, it can then be exposed to ultraviolet radiation to form a secondary image of the radical cations associated with the first. This is then metallized with a second plating solution, i.e. an iron-nickel mixture, to form sensitive cells.

If desired, this operation can be repeated with different metals, but the metal with the lowest resistivity should be deposited first.

A typical procedure of the invention is illustrated in the following examples, in which parts and parts are by weight unless otherwise indicated.

Example 1

The polyvinyl alcohol film - containing 10% percent N, N ^{, -} dimethylbipyride dichloride is exposed to ultraviolet irradiation despite a negative optical density. A dark blue image having an optical density in the range of 0.1 to 1.5 is obtained. The film was processed by immersion in a electroless plating solution at 20 ° C for 20 minutes. The development is prepared from the following water-soluble components and made up to 1000 parts.

Anhydrous sodium sulphite 20 May parts Sulphate pentahydrate sodium 30 parts silver nitrate 3.0 parts 2,4- [1,2-dihydro-2,4-dihydro-2,4-dihydro- chloride 1.5 part Anhydrous sodium carbonate 1,2 part Anhydrous sodium sulphate 40 parts Sodium tetraborate 4 • parts The last two folders -se add to the reduction-

influence of water on polyvinyl alcohol film.

After washing and drying, the blue color disappears and is replaced by a dark brown image having an optical density in the range of 0.1 to 2.2.

Similar results are obtained when sodium sulfate is replaced with potassium sulfate (40 parts or ammonium sulfate) (60 parts).

2,4-Diaminodiene dihydrochloride is replaced by an equal amount of? -Methylaminophenol sulphate ("m-ethanol"), p-hydroxyphenylaminoacetic acid ("glycine") or p-aminophenol, and good results are obtained.

Higher contrast and optical density are achieved by reducing the amount of sodium thiosulphate and increasing the pH by adding an ammoniacal solution or sodium carbonate. - The solution must be stabilized to prevent it from coming. a nonionic reagent must also be added to deposit silver by adding cationic surfactants and to prevent precipitation of the cationic agent. A suitable amount of detergent is 0.001 to 0.1 percent.

Example 2

The developer - produces a high optical density, but is not suitable for halide-containing film materials because - silver halides precipitate. The developer is prepared by dissolving the following ingredients in water and diluting to one liter.

Citric acid 20 parts

Silver nitrate 1.75 parts by weight of ammonium sulphate 4.0 parts by weight

Surfactant

Anhydrous sodium sulphate 40 parts

The polyvinyl alcohol film containing 10% N ^, N ' -dimethylbipyridine dimethylsulfate is exposed to ultraviolet light through a wire mesh grid until the optical density reaches about 2. After immersion in said solution for 10 minutes at 20 [deg.] C, washing and drying has a silver image of an optical density greater than 4 in the exposed areas.

Example 3

The method of Example 2 is repeated, but the surface of the active agent is replaced with polyvinylpyrrolidone (20 parts). With this solution, it has been found possible to use halide-containing active ingredients without undesirable veiling.

Example 4

The glass plate coated with gelatin is immersed in a 10% aqueous solution of N, N‘-dimethylbipyridilium dichloride. The plate is dried and exposed to ultraviolet light through a metal grid.

After exposure, the plate is immersed in a solution containing

Copper sulphate pentahydrate 10 parts

Sodium hydroxide 10 parts

Sodium vin-a-n 50 parts made up to 1000 parts to which 10 parts of a 37% formaldehyde solution was added. The blue image turns dark brown. After washing and drying, the density is greater than 2.

Example 5

A glass plate coated with 0.025 mm gelatin is immersed in the solution

Of N, N‘-dimethylbis (pyridinium) methylsulfate (10% aqueous solution) for one minute, rinsed with distilled water for 5 seconds and allowed to dry. After exposure for minut5 minutes through a line negative with a 100-watt mercury lamp at 50 cm, the plate is immersed in a palladium chloride solution prepared from palladium chloride (0.1 part), concentrated hydrochloric acid (10 parts) and water (up to 1000). parts). After one minute, the plate is removed, washed with water and developed in an electroless nickel plating bath prepared from the following components:

Nickel (6H2O) chloride 25 parts

Maleic acid (m-onc-sodium salt) 6.5 parts

Gluconic acid (sodium salt) 55 parts

Ammonia (solution of specific weight -0,880) to pH 9

Sodium phosphate 35 parts

In one minute a black image is obtained, the optical density of the fully exposed area is greater than 3.

The procedure described above is repeated using sequentially, as a sensitizer, 0.1 part of felt and gold chloride with hydrochloric acid (10 parts) and then using silver nitrate (0.1 part) with nitric acid (10 parts). Similar sensitization is detected.

Example 6

The procedure described in Example 5 was repeated using a palladium sensitizer, but the residence time in the nickel solution was increased to 30 minutes. The image acquires a metallic appearance and is sufficiently conductive so that it can be electroplated.

Example 7

The polyethylene terephthalate film coated with the alkyl resin based lacquer is coated with a solution containing

Poles (N, N‘-p-xylylene-4,4‘-bipyridilium dichloride) 0.5 parts

High molecular weight polyvinyl alcohol with a high hydrolytic degree of 10 parts glyoxal hydrate of 1.0 part

Ammonium chloride 0.2 part

Water up to 150 parts

The solution was evaporated to give a sensitive layer of -0.025 mm thickness. The preparation is carried out under reduced artificial lighting. The film is exposed through a line negative for three minutes under the conditions of Example 5. After exposure, it is immersed in a solution of gold chloride (0.5 parts) and concentrated hydrochloric acid (10 parts) in water to 1000 parts). for one minute.

After washing, the induction is completed by immersion in a commercially available electroless solution, nickel plating at room temperature for five minutes. It obtains a black image with an optical density in a fully exposed area greater than 2.

Example 8

A piece of the coated film prepared as described in Example 7 is exposed and sensitized with the palladium salt as described in Example 7. 5. Then wash and develop in the following bath:

Cobalt (6H2O) chloride 27 parts

Sodium citrate (2H2O) 90 parts

Ammonium chloride 45 parts

Sodium phosphate 7.5-parts

Water up to 1000 parts adjusted to 8.5 with ammonia solution.

A brown picture is obtained.

The piece is subjected to prolonged evolution (for 45 minutes) and then further evolution at a high temperature (~ 80 ° C, for 3 minutes). In both cases, conductive cobalt films are obtained.

Example 9

The glass plate is coated, exposed and sensitized as described in Example 5. After washing, the gelatin layer is produced by formaldehyde treatment (for 5 minutes in a solution consisting of the following components:

Formaldehyde solution (40%) 10 parts

Sodium carbonate (anhydrous) - 5 parts

Water up to 1000th parts

It is then developed in a subsequent bath for three minutes at + 80 ° C.

Cobalt (II) chloride (6H2O) 60 parts Nickel chloride (6H2O) 2 parts Sodium tartrate (4H2O) 200 parts Ammonium chloride 50 parts Sodium phosphate 17 parts Water to 1000 parts Ammonia do pH values 9

A thick black image is obtained.

Example 10

The plate - was coated, exposed - and sensitized as described in Example 5 and then developed for ten minutes at room temperature in the following solution.

Ferrous sulphate (7H2O) 120 parts

Sodium Sitrate (2H2O) 170 parts

Ethylenedetaminetetracetic acid - 50 parts Sodium phosphocman 8E> parts

38%. formaldehyde solution 220 parts

Water 800 parts ammonium hydroxide solution to pH 10

A thick black image is obtained.

Example 11

A solution of diphenylpytylhydrazyl (2% in acetone) was used to form a loop on a piece of polyvinyl alcohol film, which was then dried under a nitrogen atmosphere. The film was sensitized with a 0.1% palladium (II) chloride solution and then developed in the retention solution as described in Example 4. After five minutes, the image became dark brown in color. After 30 minutes, the image is metallic and has a resistance of about 200 ohm / cm 2.

Example 12:

The open-pored polyurethane foam is impregnated with a solution comprising:

Polyvinyl alcohol 20 parts

N, N‘-dimethylbipyridilium methylsulfate 1 part

Water up to 1030- parts

The foam is drained, dried and a free radical is formed by heating to 100 ° C for 30 minutes. The foam is then immersed in the plating solution described in Example 4 and the reddish-brown copper deposit formed in the foam is then conductive.

Example 13

The surface of the phenol-formaldehyde laminate piece is roughened, for example, by abrasion with a sandpaper, coated with the following solution and dried.

Polyvinyl alcohol 10-parts (crosslinker)

Glyoxalhydrate 1 part

Paraquat dichloride 0.5 part (cross-linking catalyst) Ammonium chloride 0,2-parts

Water ... 120.-, parts

After exposure to ultraviolet light · - - despite the negative of the printed circuit board, the cardboard develops in a subsequent bath for 30 minutes at room temperature (20 ° C).

Copper sulphate pentahydrate

CukO4.5H2O 10 parts

Vinan - sodium potassium 50 parts

Sodium hydroxide 10 parts

37% formaldehyde solution of IQ parts

Water 100- parts

The resulting copper - coating - has a resistance - of less than 1 ohm / cm ² and its thickness can be further increased by electroplating or further immersion in the above-mentioned solution. Thicker layers of copper (0.0025 to - 0.005-cm) can be obtained by conventional techniques.

1 6 1 5 4

Example 14

The alkyd resin-based polyethylene terephthalate film is coated with a solution containing

N, N‘-p-cyanophenyl-4,4‘-bipyridilium dimethosulfate 1.0 part

High molecular weight polyvinyl alcohol, high hydrolytic degree of 10 parts

Glyoxal 0.5 parts

Sulfuric acid up to pH 3 to 4

Water up to 100 parts

The solution was evaporated at a temperature not exceeding 75 ° C to give a sensitive coating of 0.003 mm thickness.

The preparation is done under dim artificial lighting. . The film is exposed to electrons from a scanning electron microscope. Electron energy varies between 10 and 80 · keV. The spot size determined is 0.2 to 0.5. μΐη. The image color is dark green. After developing in the plating solution of Example 1 for 5 minutes, the exposed film has a normal line pattern. It was differentiated. 2000 pairs of lines per mm.

With prolonged exposure to electrons, the image becomes red due to the formation of a neutral compound and may also be. plating with the solution of Example 1.

Example 15

The coated polyethylene terephthalate film was prepared as described in Example 14 and exposed to ultraviolet irradiation in an electron spin resonance spectrometer. A green coloration of the radical cation is formed. spin concentration increases linearly with exposure times up to 2.5 X 1015 spins / cm ² . The optical density is 0.5 at 610 nm. The radical cation image is immersed in the plating solution described in Example 1 and is achieved. with a very dark brown image having an optical density greater than 4.

Example 16

The coated polyethylene terephthalate film was prepared as described in Example 14 and exposed to electrons in a scanning electron microscope at an energy of 50 kev. The exposed film has an optical density of 0.5 at 610 nm and a radical concentration of 1.4 X 10 10. ¹⁰ spins / cm 2 as measured by electron spin resonance. After immersion in the plating solution described in Example 1, the image is examined by electron microscopy and exhibits a resolution of greater than 1500 pairs of lines / mm.

Example 17

The coated polyethylene terephthalate film was prepared as described in Example 14 and exposed to ultraviolet radiation. through a metal grid to create a green one. .radical cation image. The electroless plating solution has the following composition:

Solution A

Ammonium sulphate 78 parts Ferric nitrate 8 parts Citric acid 10.5 part Surfactant 0.2 part Dodecylam-in 0.2 part Water to 1000 parts

Solution B

Silver nitrate Water

8.5 parts to 100 parts

Prior to use, one part of solution B was mixed with nine parts of solution A. After immersion in this solution for five minutes, a black image was obtained.

Example 18

An aqueous solution is prepared. 3 parts of polymer containing unit-structures

And - 15 parts of polyvinyl alcohol.

The film formed forms a blue or purple radical cation on the glass plate. image when exposed to ultraviolet light. The image is developed with the plating solution of Example 1 to form a black image.

Example 19

A polymer is prepared from p-xylylene dichloride and 2,2'-bipyridyl. The polymer consists of repeating. units

cF

The polyvinyl alcohol film containing this polymer rapidly rearranges the blue color when exposed to sunlight and immerses it in the plating solution of Example 1 to give a black coating.

Example 20

The film is cast from a solution containing 10 percent. polyvinyl alcohol, 1% N, N‘-bisphenyl-2,7-diazapyrin difluoroborate, 0.2% ammonium chloride, 0.5% glucose. Film exposed to light of wavelength. to at least 436 nm gives a radical cationic image that turns black upon immersion in the plating solution of Example 3.

Example 21

The film is cast as described in Example 30 using 1,2-bis (1'-methyl-4'-pyridinium ethylenedimethylsulphate) and a purple image is obtained in sunlight when exposed through a metal grid. described in Example 3.

Claims (5)

1. A method of activating organic materials, in particular based on water-soluble or water-swellable polymers, prior to electroless plating, characterized in that a cation-derived activator is deposited on or on the substrate wherein R1 to R12 is hydrogen, or an organic group of zero or an integer. 2. A method according to claim 1, wherein the cationic activator is selected from the group consisting of 4,4'-bipyridylium, 4,4'-bicholinium, 1,2-bis- (4- pyridyl) ethylene, 2,7-diazapyridinium, 2,2'-bipyridyl or 4- (4'-pyridyl) pyridinium cation. 3. A method according to claim 1 or 2, characterized in that activating agents derived from at least one cation of formulas 3 to 47 are deposited in or onto the substrate. C3) 4,4‘-bipyridylium · (P) (4) 4,4‘-Bichlnolinium (Q) (5) (also (7) O 1,2-bis (4-pyridyl) ethylene (E) 2,7-diazapyrinium (A) 2,2 ^, -bipyridyl (B) 4- (4‘-pyridyl) pyrldinium (M) where R stands for: [9] —CH3, X = Cl, Br, SiFe, HSO6—, CH3SO4— (10 ·) -CH2CH. X = Cl Italy (11) -ch ^ chRS) X = Cl (12) X = Cl OCH $ CH * (13) -що ⁰ © X = Cl / c ^ c (14) X = Cl (15) X = Cl (16) —CH2CO N (C2H5) 2 X = Cl (17) - ^CH 2 - X = Cl (18) -CH _Z CO ΝΗ — ζθ ° X = Cl (19) —1CH2CO NH-t-but. X = Cl Italy (20) -. (OH2JCOCH3 X = Br Italy (21) —CHZCHÁCH X = Cl i-prop Italy (22) - (CH 2) n CON ' X = Cl \ 1-prop Italy (23) -ch ^ o νη- ^ Ο ^-0 ^ ³ X = Cl (24) —CH3COOC2H5 X = Br Italy (25) - © -CN X = Cl Italy (26) OCHj X = Cl Italy (27) X = Cl (28) ~ ^ / qc _from h _p X = Cl (29) 32> X =. Cl t-but = tertiary butyl i-prop = isopropyl (30) CH3 — P further M — R ‘X where R‘ is (31) - ^ q ^ nhcoch X = Cl (32) ^- © ^Oc X = Cl United Kingdom (33) —CH3 X = C1 further (34) CH3-Q-CH5 (CH 2 SO 2) 2 (35) (BF4-) 2 (36) CH 3 —E — CH 3 (CH 3 SO 4 -) 2 CH2 / 1 (37) в 1 (Cl -) 2 \ l CH2 (38) <^ сн _г -₽-снн @> 2 ~ C1 Italy (39) CH 2 P-CHCl ³ 2-C1 (40) CHg -> - CH ^ P- ^CH X Xrgy ^eH 2- ^₽ - ^CH 3 Z ''' 0CÍ ” (41) (43) (47) —OOC COO 4CI where В is a base such as pyridine, quinoline or monoquernizoinated bipyridyl (M), (44) (45) 4. Method according to claim 1, characterized in that the substrate is contacted with a sensitizer, which is a solution of a platinum group metal compound, in particular a solution of a palladium compound, prior to depositing the activating agent. or a solution of a silver compound or a gold compound. 5. The method of claim 1, wherein the cation-derived activator component of the compound of the formula: