NL8002423A - METHOD FOR FORMING AN ADHESIVE METAL SURFACE ON A SUBSTRATE. - Google Patents

Description

Jfc 4 "Method of forming an adhering metal surface on a substrate".

There are many applications where it is desirable to form thin metal films or coatings on various solid substrates. An example of such application is the manufacture of silver-plated mirrors, in which very thin films or coatings of metallic silver are deposited on glass from chemical solutions. or similar substrates. Large reflectors for solar applications are also manufactured by depositing silver or aluminum from vapor on solid substrates.

Some of the problems associated with the prior art methods of forming thin metal coatings on solid substrates are the laborious application methods, for example, in manufacturing silver-plated mirrors from chemical solution and the inability to maintain the metal coating for a long time. the solid substrate. Also, in vapor deposition, vacuum metallization, ion plating, spraying and similar methods, the metallized surface can retain its aesthetic value only if the substrate has been pretreated with some preparation, which scratches, pits and voids in the solid substrate can mask or cancel. Such materials are generally curable organic coatings which are initially applied to the solid substrates in such a thickness that they physically fill the scratches, pits and voids and then cure. The metallization then takes place on the surface of the organic coating. Unfortunately, due to the presence of these organic "undercoats", the manufacturer is faced with a number of problems regarding the 800 2 4 23 t-2 adhesion between the basecoat and the solid substrate and the basecoat and the thin metal film or coating. This problem increases considerably if the object to be manufactured has to be used outdoors and is subject to the weather.

Therefore, there is a need for a better method of forming adhering metal films or coatings or solid substrates and for better metal-coated articles.

The invention now relates to a better method for adhering a thin metal film or coating 10 to a solid substrate. In this better method, a specific silan or mixture of silanes is used to strongly adhere the thin metal film or coating to solid substrates.

It has been known for a number of years that silanes can be used to bind many substances to many different surfaces. It is generally believed that silanes are not universal coupling agents, so that any given silan would bind a variety of substances to a variety of substrates. On the other hand, it is generally believed that one uses specific silanes comb for the attachment of specific substances to specific substrates, i.e. the silane must be appropriate for the application and it should not be assumed that all silanes can be used in all applications.

British Patent 1,550,532 teaches that thin films or coatings of metal can be adhered to plastic substrates using a combination of alkoxysilanes, alkyl silicates and copolymers of alkyl acrylate or alkyl methacrylate with hydroxyalkyl acrylates or hydroxyalkyl methacrylates. This British patent says that the inventive preparation described therein serves two purposes, namely the polymer is a film former and the silan enhances the adhesion of the metal over-coating. The alkoxy silanes discussed there have the formula R Si (OR '). n 4-n wherein η is 1, 2 or 3, R represents a hydrocarbon group of 1 to 6 carbon-35 atoms and R 'represents an alkyl group of 1 to 4 carbon atoms 80 0 2 4 23 • * 3. This known material and this known method are very satisfactory insofar as the objects are to be used indoors.

However, it has been found that this material exhibits insufficient adhesion of the deposited metal to the polymer film, resulting in the metal metal film becoming detached.

It has now been found that the adhesion of thin metal film to various substrates can be improved by using certain slanes and silane mixtures on certain substrates, such as the articles made according to the invention are durable and weather resistant and glossy and better reflective.

Thus, the invention relates to a method of forming an adherent, continuous, thin metal surface on a substrate and the objects obtained thereby. According to the method of the invention, an adhering metal surface 15 is formed on a substrate, in which (I) a solid substrate is treated with at least one organofunctional silane or a petroleum hydrolyzate thereof, of the general formula 1, or a mixture of such organofunctional silane or the partial hydrolyzate thereof with a second silan or the partial hydrolyzate thereof, which has the general formula 2, in which formulas R represents an alkyl radical of 1-4 carbon atoms, R "a difunctional hydrocarbon radical of 1-12 carbon atoms or a radical of formula 3, X represents an amino group, a radical of formula 4, a mercapto group, hydroxyl group or chlorine, R "represents a phenyl radical or an alkyl-radical with 1-4 carbon atoms and a and b are 2 or 3 each, c is 0 or 1 and a + c is 3, (II) dries the silane treated surface until most of the volatiles are removed and then (III) on the silane treated the surface deposits a metal to form a thin continuous film or coating.

30. The organofunctional silanes used in step 1 have the general formula 1, wherein R represents an alkyl radical of 1-4 carbon atoms, R 'represents a difunctional hydrocarbon radical of 1-12 carbon atoms or a radical of the formula 3 and X represents an amino group, a radical of the formula IV, a mercapto group, hydroxyl group or chlorine. R is preferably a methyl-80024 23 4 radical. a is 2 or 3, c is O or 1 and a + c is 3. Thus, formula 1 includes organofunctional silanes of formulas 5 to 14.

It is noted that the invention also includes the partial hydrolysates of these organofunctional silanes. By "partial hydrolyzate" here is meant the water-soluble or water-miscible product, which is formed when the organofunctional silan is treated with water under hydrolysis of all or part of the alkoxy groups on the molecule. Sometimes to obtain hydrolysis a small amount of acid is required in addition to the water.When talking about "hydrolyzate" or "partial hydrolyzate" this means that it is the hydrolysed silane or the hydrolysed silanes, water for the hydrolysis and the alcoholic solvent, which is separated off by alkoxy groups of the silan.

The substrate can be treated with the organofunctional silane or its partial hydrolyzate alone, but the invention also includes a mixture of the organofunctional silane or its partial hydrolyzate with an organosilane of the general formula II, wherein R has the above meaning, R "represents a phenyl radical or an alkyl radical of 1 to 4 carbon atoms and b 20 is 2 or 3. As indicated above for formula 1, the partial hydrolyzates of a silane of formula 2 are also part of the invention. preferably methyl.

The organofunctional silanes and organosilanes are commonly known silanes and it is believed that their preparation is sufficiently described in the art and does not need to be repeated here.

If it is required to use a mixture of silanes, such a mixture is prepared by a simple mixing method. The net silanes can first be mixed and then hydrolyzed, but they can also be hydrolyzed separately and the hydrolysates then mixed together.

When a mixture of silanes is required in the invention, it is usually preferred that they are mixed, by weight, in a ratio of 1:10 to 10: 1.35 organofunctional silane to organosilane. The ratio is 800 2 4 23 Λ 4 5 based on the weight of the hydrolysis silanes.

As indicated above, some silanes require the presence of a small amount of acid to improve hydrolysis. Such acids are, for example, hydrochloric acid and acetic acid.

Such a requirement is generally known in connection with silan hydrolysis.

It is generally preferred that the silanes be hydrolyzed before mixing. After the silanes have been hydrolyzed, simple shaking by hand of the hydrolysis vessel, viz. A bottle or flask, is sufficient to continue the hydrolysis reaction. Generally, the hydrolysis mixture is used at this point without further modification or purification.

The total amount of silan in the hydrolysis mixture can be from 0.01 to 35% by weight.

Although the silanes can be used as such, they can be dissolved in solvents which are soluble in or miscible with water such as isopropanol, methanol, butanol, methyl cellosolve, etc. Mixtures of such types of solvents are also included in the invention. These solvents can also be used with the hydrolysed silanes to increase the film-forming capacity.

The silanes or silan solutions can be applied to the substrate in any convenient manner. Methods such as dipping, flowing and spraying are most suitable for the invention.

The substrates to be used in the invention are solid. Thus, almost any solid can be the substrate of the invention. Such substrates are, for example, plastics such as acrylic-zuumitrile-butadiene-styrene copolymers, Sioplas, cross-linked polyethylene (Dow Corning Corporation, Midland, Michigan), polycarbonates, polyethylene terephthalates such as Mylar (EI DuPont, Wilmongton, Delaware), polyimides such as Kapton (EI DuPont ), polyphenylene oxides such as Noryl 30 (General Electric Co., Pittsfield, Massachusetts), polyphenylene sulfides such as Ryton (Phillips Chemical Co., Chicago, Illinois) and mineral-filled nylons such as Minion (EI DuPont), acrylic products, urethanes, epoxy products and polyesters, to name just a few. Wood, cardboard, glass, metals, silicone rubbers and resins, urethane foams and polyvinyl chloride foams are examples of 800 2 4 23 •% 6 other substrates to be used.

A method described herein consists of treating a solid substrate with an organofunctional silane or a mixture of an organofunctional silane and an organosilane, after which the silane-treated surface is allowed to dry until most of the volatiles of the treated surface removed. By volatile substances is meant the solvents, water and the low molecular weight products formed on hydrolysis. By the "majority" of the volatiles, it is meant that the surface must be tack-free or substantially tack-free on contact with the finger. This can be achieved in a number of ways. For example, the treated surface can be left to stand for a certain time at room temperature, perhaps several days, to allow slow evaporation of the volatiles into the atmosphere. However, since time is a factor in industrial manufacture, it is possible to heat the articles to remove volatiles. A vacuum can also be applied in order to reduce the pressure and to promote evaporation. A number of methods for removing volatiles have been tried in a short time, for example 20 1-5 sec. by simultaneous heating and application of vacuum.

Any method of removing volatiles that fits within the manufacturer's manufacturing method is within the scope of the invention.

After the volatiles have been removed, the thin metal coating is applied. In general, any method by which continuous metal coatings can be applied is suitable for the invention. Methods such as vapor deposition, electroplating, splashing, ion plating and spraying are preferred. Application of the thin, continuous metal coating, however, can be accomplished with current chemical solution application methods without detrimental effect on the adhesion promoting coating.

Metals which can be used in the invention are all kinds of metals which can be deposited from vapor, electroplating, splashing, ion plating, spraying or applying from chemical solution. Metals such as copper, nickel, tin, silver, silver, solder, gold, aluminum, platinum, titanium and zinc and chromium are preferred.

In the invention, "thin" means the thickness of the metal film required to obtain a continuous, cohesive film or coating. Generally, these coatings are less than 30 microns thick.

The articles prepared in accordance with the invention can be coated by clear protective coatings such as the silicone resins described in U.S. Patent No. 10 3,986,997. These materials are commonly referred to as "overcoats" and are well known.

As mentioned earlier, the surfaces of some substrates are so soft that they can be damaged by dents or scratches during the manufacture of the article and in order to obtain an aesthetically pleasing product, the damage must be eliminated, otherwise damage to the metal layer will be avoided. continues to see.

A common way of covering the damage is to apply a primer or undercoat 20 to the substrate and a material such as curable organic polymers.

The organic polymer fills in the damage and gives a smooth, flat, damage-free surface over which the thin metal coating can be applied.

The invention therefore relates to the use of such undercoats in combination with the method and materials of the invention. The invention therefore relates to treating a substrate with an undercoat and applying the silan or silanes of the invention to this undercoat. The metal is then applied to the silan-treated undercoat or primer. Preferably, undercoats or basecoats of certain polysiloxanes are used. The particularly preferred primer is a siloxane coating as described in U.S. Patent 3,986,997.

When using an undercoat, the substrate is cleaned in some convenient manner, after which the 800 24 23 δ undercoat is applied and cured. Generally, a coating of U.S. Pat. No. 3,986,997 requires 6-8 hours at 150 ° C to apply. Such undercoats need only air dry for a few minutes. Under certain circumstances, depending on the substrate and undercoat, a primer may be required. As such primers, one can use, for example, the silanes of the invention. The cured undercoat is then covered with the silan or the silane mixture, dried and then coated with the selected metal. Thus, the invention also relates to the subject substrates, which are coated with an undercoating of organic matter or silicone and then treated with the inventive silanes or silane mixtures.

A third aspect of the invention is the use of the silanes of the invention in combination with certain curable coatings to improve the adhesion of thin metal films or coatings. While the essence of the invention is the treatment of certain substrates or the treatment of certain substrates provided with an undercoat of curable organic matter or silicone, this further aspect of the invention relates to metal coating of curable organic or silicone undercoats, in which, before curing, the present silan or silanes are incorporated.

The invention therefore also relates to the incorporation of the silanes of the invention into the curable undercoat and the deposition of metals thereon to form films or coatings. The invention therefore also relates to a method of forming an adhering metal surface on a substrate by (I) treating a solid substrate with a curable organic or silicone undercoat containing at least one organo-functional silane or partial hydrolyzate thereof with the general formula 1, or a mixture of such organofunctional silan or its partial hydrolyzate, with a second silan or its partial hydrolyzate, which has the general formula 2, in which formulas R represents an alkyl radical of 1-4 carbon atoms R 'represents a difunctional hydrocarbon radical with 1-12 carbon - 800 2 4 23 • if Λ 9 atoms or a radical of the formula 3, X represents an amino group, a radical of the formula 4, a mercapto group, hydroxyl group or chlorine, R "represents a phenyl radical or an alkyl radical of 1-4 carbon atoms and a and b are each 2 or 3, c is 0 or 1 and 5 is a + c 3, (IX) the undercoat to be dried and until most of the volatiles have been removed and then (III) depositing a metal on the undercoat to form a thin continuous film or coating.

The organic undercoats to be used are those currently used as undercoats in metal deposition on solid undercoats. These fabrics are air-drying acrylic products or urethanes, which can be used with or without heat curing. Such a material is, for example, EB-1, the trade name for an acrylic polymer, which is manufactured by Red Spot Paint and 15 Varnish Co., Inc., Evansville, Indiana.

The amount of silan or silanes included in the undercoat is 0.1 to 10% by weight, based on the weight of the silan or silanes and the undercoat. Simple mixing of silane in the undercoat is all that is required. It should be noted that such mixing does not need to take place under anhydrous conditions, since the adhering effect occurs when the silanes are used as such, as when they are used in a pre-hydrolysed state. Depending on the intended application, the bottom coating is dried and / or cured, after which the metal coating is applied by one of the aforementioned methods.

Articles made according to the invention have better adhesion, weathering resistance, durability, effectiveness and reflective metal surface.

The following examples illustrate the invention.

A number of silanes were evaluated by examining the adhesion of the metal coating. A subjective assessment of the appearance ut was made, based on properties such as film continuity, gloss, mirroring and the presence or absence of voids, dents, etc. A film is excellent when it is continuous without cavities and / or dents and is shiny and strong 800 24 23 10 reflective. Reflective is an expression used in the mirror surface art and refers to the amount of light transmitted from the mirror surface, i.e. how good the mirror properties are. Adhesion or adhesion was measured subjectively by rubbing the metal surface under moderate pressure with a cloth saturated with acetone, methanol or isopropanol unless another method is indicated. The extent to which the metal surface survived this treatment has been reported. No coating removal is considered "excellent." "Good" is when some slight wear occurred. "Fairly" means significant metal removal. "Bad" means removal of almost all of the metal coating. "None" means that all upholstery was removed.

Example I

The following samples were prepared to determine which silanes or combinations of silanes give the best adhesion between a given substrate and certain metals. Silanes or combinations of silanes at the indicated concentrations were prepared by a process involving hydrolysis of each silane and optional combinations of silanes to obtain the adhesion promoter used on the substrate. Table A shows the different silanes tested in this example.

Silan Ά is the compound of the formula 5, silan 25 b the compound of the formula 7, silan C the compound of the formula 6, silan D the compound of the formula S, silan £ the compound of the formula 15, silan F the compound of the formula 16, silan G the compound of the formula 17 and silan H the compound of the formula 9.

The results are shown in Table B. IPA means isopropanol and MeOH means methanol.

Primer preparation.

8 g of silan A, 8 g of IPA and 1.12 g of water were mixed with stirring in a small 30 ml glass vessel fitted with a screw cap. The vessel was left overnight, 16-20 hours. The material was then diluted with 800 g of IPA after transfer to a larger bottle.

12.35 g of silan B, 717.65 g of IPA, 30 g of ice-5 vinegar and 40 g of water were mixed together in this order.

24 g of silan C and 1.2 g of water were mixed together and left to stand overnight, 16-20 hours. This material was then diluted with 800 g of MeOH.

Silanes D, E, F and G were all treated in the same manner. 3 g of the silan was treated with 27 g of MeOH and then a small amount of acetic acid and sufficient water for complete hydrolysis were added, the mixture was shaken until clear and then used without undue agitation.

H was used in an amount of 20% by weight in 15 MeOH using the same method as for D, E, F and G.

All primers were filtered before use.

All samples were dipped by hand in the primer solutions and excess material was allowed to drain.

The samples were then dried as shown in the tables.

Table A shows the silanes or combinations of silanes used in the examples. "Sample number" is the reference number for the corridors used in the examples.

"Silan 1" is the organofunctional silan used in the sample.

"Silan 2" is the organosilan used in the sample. "Added acid" and "added water" mean that the material was used as hydrolyzate in the hydrolysis water in addition to the alcohol produced in the hydrolysis. used as such, ie without prior hydrolysis, this is indicated.

In Table B, the sample number of Table A indicates the silan or silanes used in the particular run. If more than one run was performed using the same silan but with a different substrate or deposited metal, the run is designated a, b, c, etc. For example, in Table A, Sample 4, there is a primer prepared from silanes C and D. In Table B, sample 4a 800 24 23 12 indicates that the silanes were used in a 2.4: 1 ratio, with 1.3 wt% total silan being present in the primer, the substrate at the hallway was glass and the deposited metal was silver solder. Sample 4b of Table B shows the primer of Sample 4 of Table A with the same ratio of silanes at the same weight percent solids, but the substrate is now acrylic sheet and the deposited metal is aluminum.

All samples of Table B were vapor deposited using a Mikros Vacuum Evaporator Model VE-10 10 manufactured by Thermonics Laboratories, Hayward, CA.

Example II

In order to compare the material of British Patent 1,550,532 with that of the invention, the following material was prepared. 180 g of a silicate-based polymer containing methyl trimethoxysilane were mixed with 20 g of Acryloid OL-42 (Rohm & Haas Co., Philadelphia, PA). Acryloid OL-42 is an acrylic polymer, which is the same as in Example 1 of said British Patent. The Acryloid is 80% solid in cellulose acetate. 1 g of hexamethylene tetramine as a catalyst was also added with stirring.

A primer (P) to be used was prepared, consisting of 8 g of the compound of the formula 6, diluted with 800 g of IPA and 24 g of a 40% MeOH compound of the formula 11, diluted with an additional 800 g of 25 MeOH. 75 g of the diluted compound of the formula VI are mixed with 25 g of the diluted compound of the formula II and a small amount of acetic acid and water and the mixture is stirred until clear.

A Lexan (General Electric Co., Schenectady, NY) polished polycarbonate sheet with emerald paper to mimic a production failure product. After the slide was cleaned, a labeled subdivision into four sections was applied to the slide and dipped a portion in the above primer solution (P) and allowed to air dry for 20 min at room temperature.

Then the solution of acrylic polymer, 800 2 4 23-3 * 13 silicate and alkoxysilane, analogous to that of Example 1 of British Patent 1,550,532, was applied to 3/4 of the wafer and also as overcoat on the 4 primed and allowed to air dry. The coating was then cured for 5 minutes at 70 ° C and 20 minutes at 100 ° C. Then 1/2 of the plate was immersed in a solution of P and the immersed portion was allowed to air dry at room temperature for 10 min. Finally, metallic silver was deposited on the entire plate from vapor and cured at 100 ° C for 15 min. If one places the plate on its side and examines the coverings or layers on the plate, the left-most 1/4 section (marked A) has only a silver coating.

To the right, the next 1/4 portion (designated B) has a silver top coat, which covers the polymer of British Patent 1,550,532, which in turn covers the polycarbonate wafer. The third 1/4 section (denoted C) has a top layer of silver, which covers a layer of P primer, which in turn covers the polymer of British Patent 1,550,532, which in turn covers the polycarbonate sheet . The last 1/4 section (denoted by D) consists of a top coat of 20 silver, a second coat of primer P, a third coat of the polymer of British Patent 1,550,532 and finally a fourth coat of primer P.

Sections B, C and D were shaded with a sharp instrument with scratches, creating 25 equal squares. Thereafter, the cross-hatched squares of Scotch Brand adhesive tape No. 650 (3M Co., St. Paul, Minnesota) were pressed and forcefully removed. Noting that the most optimal conditions had not been taken into account, the test was considered successful if at least 50% or more metallic silver remained intact. Table C30 gives the results.

Example III

A silicone resin according to Example II of U.S. Pat. No. 4,173,553 was prepared with the proviso that the compound of Formula 7 was present in an amount of 8 0 0 2 4 23 14 of 10 wt%, the compound of Formula 18 was present in an amount of 40% by weight and colloidal silicon dioxide was present in an amount of 50% by weight, based on the weight of all three components. This material is indicated here as "A". sample of silicone resin according to example I of the

U.S. Patent 3,986,997, i.e., the same material as above, but without the compound of Formula 7, and this material was designated "B". Both materials were compared side by side for their ability to receive and adhere metal deposited thereon. Both materials were diluted to about 10% solids with isopropanol.

A clean square of Lexan polycarbonate 1/2 was dipped in "A". The remaining 1/2 was dipped in "B". The sample was then air dried at 25 ° C for 40 min. Silver was then applied to the sample by deposition from vapor. The sample was then cured at 125 ° C for 1 hour. Both samples showed excellent mirroring. The samples were rubbed with methanol to test the adhesion of the silver. The material "A" was clearly superior in holding the metallic silver.

20

Example IV

The silicone resin designated "B" in Example III was coated on a clean Lexan polycarbonate square and cured at 100 ° C for 25 min. Then half of the coated plate was dipped in a primer previously designated as primer P of Example II and allowed to dry for 2 min at 25 ° C. Silver was then deposited on the plate from vapor and cured at 125 ° C for 1 hour. The half side of the wafer treated with primer P of Example II showed better retention of the deposited silver.

The methods of retal deposition described here are the usual methods of depositing metals, and it seems that extensive descriptions of such deposition methods are also unnecessary.

800 2 4 23 15 φ Ο <0

+ J Cl C I I

μ o ®Bjiie <dieffl <üiöfOnJj 3> C i ~> I -n * n t ~ i -η m · η -η · η I

2 0) N Ci Φ o P Ό μ S '(OnJieiCBJiOfCnJnJiÖ®® Ο Ο τι · η τι -ο · η · η η · η · π τη · η -n Μ> (β QJ% Di r-i «Ό Ό

CPI sss s ® a K

δ I I iriJÖOOrtOOOO

n yy I I | & QQ) <UftC> Ve) <U

3 0 I i IHS'ESHSSSS

ft 0 o> W r-i § § s s s

g -i << 00 <Ci << 0! j J

OH'HHSSHWHS I I I> Ή 0 ft 0 o>

CM

c

I I I ISHbOnHfeOK

• H

W.

r4 rj

ic rtxiüUWrtört * I I * • —I -H

w u Φ

to O «-I <N

C * τ-ίΓΜΠ «3 <ΙΛ (£ ΙΓ'00σΐ · ^ '^ -' êë 800 2 4 23 16 I" c d> 0) 01 c in H <0 in ·? M on m nmnro

It ^ H * “'* 4-) u in 0 -k O' C ^

• H

'O c £ φ «-Η * H« -Η * ~ 1 * - <* -l »-« Λ fj III **** ** ·· ·· ·· ° O (fl 04 II I'tf' tf Tf ij H III ·· * * '' '' QJ ^ IC 04 04 04 04 04 04 0> «0 'X <<<<<< <<<<Ό O' Ό Ό g

c C c HI

5 xa) a>. * -¾ XJ 1— »Μ · Γ") w Δ · Η ω Ό OJ -Η Ό * 0 * 0 * 0 · £ Ü.-4 -PC> -PHV ®SSPi ο o « o «o> ο ο ο o 4-j λ E4Ju +) B de * ο» ο »* hc 3 -w -μ B o <0 a DD +> ** u - (- 1-1-)

O UUU 1-1 * k m Τ '-H

• O * 0 * 0 * 0 -k Λ U -Η Ο -k U Λ U

C C in CO CO CO Λ U Ο ΛΟ Λ0 0 W fl> -riin fiin »nn 0 B S 2 2. 2 Ϊ 2 Ό E pco geo> 4C0 ^ co

Jill'S. -Γ-1 »30 33 3 3 W xj G 0-k0f-'0-ri0f-'d) 3 3 CQ cn <U njoi-Hn-rin-HO) ·“ · r * ^ C -k O '\ \ J3 \ A \ Λ \ π \ \ r1. .

^ C k C CUCUGUfiUO) · U COCUCCJ c u

Λ Ό ΟΙ τΙΟ -kO -HO -HO ID C 0 -HO -kO -HO -WO

4J Ό ΕιηβιηβιηΒΐηΟ'-Ηΐη £ m gin S j £ j gin W -r-1 k 04 04 04 04 β 04 04 04 0104 a-Hioomoom ο ο ο ο ear η-οπτιητιη-η mm mm mm mm -k - k -k -k -k -k -k -k -k ΛΛΛΛ Λ A Λ Λ Λ 5 ο § ρ § § § 4-) Λ O 'Iklklklk-kk -k -k -k

C) H C kdlkdlkOkOCfi C C 3 S

NlU-k (UQ) 00) CIO Q) 0) -k-k -k -k -k 0

a> <e ό> 'd>' a> O>, o§s g g S P

-'-PC) Hi-I I-Ir-I f-li-I r-lr-l 3 3 3 3 3 H

Ή d) <k -HO-kO-kO-kOfkf-j Η H rj Λ <g Ai NIONMNCONinrOlO e «3 W u

O '* k I

4J. k to 3 6 <β I — I 0 * k »Q CO 3« J d) CQ ιί in ci ^ -k

k> '- kOk ^ .i CC

+ J HSe-kOrDCHO-kH

OJ ID ID ID ID> t E- <C β Λ! > 0 § ÏÏ

xi re re kW «kWtySk -P w C 3C

3 rH rH rH r-l U (β ij X »0 ^ -1 -k (/ 1 O 'O' 01 O 'Ö (ï.Sü <kJU μ ··«. Ut k d)

Ink ιβχιο 2 ω d-ι o cn «η cn m ^ rr £ 80 0 2 4 23 17 ri m m« - <’“ l **! , -T * - * - ^ -?. »T.» «~ yy 4f« lö vO U VD VO W VO ®

O CM CM O O O O O © O O

<< <H rfC <<M << 10¾¾¾'O 9 § § s s §§ | -S-ï SS S ό S 2 si's

5¾¾ ss ags 8 III

O 4_) + j 4J4J WO'-P O 'Di + JDi ^ * W * rl iH * H h U 3 3 3 3 3 3 0)

W u 1-, -n now U U U O U υ U

«'° o SoU 2oü Λ ° ο ° m ° m * ° m ^ Λ ° ο · ° ο · ° ο ά 52 Λ« J2 ΪΞ 5- 5 ^ 52 52 5 “§ β | I I Eïï ε β · η β -Η S ιηΐ? Β Ε 6 co Λ ω Λ 03 Λ α> Λ ° ^ g Λ ^ νο Λ ο 9 ° £ ™ ί? \ ”\ Λ \ 'cu's.u \ U' v. U CU β U CU β U "^ rP 5oU · 5εΡ I λ <20 c * Ο C0 ** 40 * Η0 * Η0 · Η0 30 * yy0 E ° m 5¾} -η in η in e ί £ ϊ ε id ε E JQ ε cm E cm E cm sm Hcm 8cm cn o cm Q cm q cm 8cm qcm qcm rn i-> in -n in η in τη ιο η η · η 10 n '• O -ri NI? Njnj 5 Λ Λ Λ A Λ Λ Λ ΑΛΑ

II I

ί I * 3 5 $ * $ 2 111 η 3 §η η η η η! j! hh t «« Ν Ν Ν Ν Ν ΝΝ <0 r * I · 01 I β I Η Η Or U J | >, I (0> 1 C> Τί * <0 ω CU Η Λ 0 «ο ^ ίίι ÏÏ Η ω η c -8 is 3 c Ε, c ο ~ ® (ΰ Oic5> iCiO <Ö + ί * Η id 5 -S'S ^ oS s ^ -m § & 2.3¾ sog'lll '1 »£ 5 * 33 Λ ft 0-sis a ^ -s r3 H0 * ft (5 ft Η Λ 4) 01¾ Ih Q ft ΛΗ -η X HSÖ 0 ft $ ^ »5 m · m · m · 80 0 2 4 23 18

in in in in «hOOO

* 1 2 * »% 3% ο 1 2 ο ο« - · ο — 1 * Η Ή * - »1-4 1-Ι 1-« «-1« Η, Η I1 Η «« «<« 1 II »II» 1

α> οο co 1η 1 · co I j | j j J

* »1«> 1 «1 I I I I I I 1 o o o o CS o <<<<< 1 <1 $ 1 & <<<<< Ό Ό Ό Ό Ό Ό Ό, -. g β β β β β β

O'. 0) 010 (1) 0) 4) (1) XX

SjijjZisxxxx'Ot-ii ~ \ +) s 4J1JOJ4J4J4J4JOHH 0 0 0 h ejainieoiwwO'SSO.S.®! O +) +) +> +> +> +) + J ε β O 'O' h -> -) τ-C 1r4 '-C 1 -) “- (1— (<0 (0 03 ^ 3333330 +> +) «Ij uuu υ auuuuuaau ω 00000 10 10 000 10 100 m · 0 · Ο» Ο · Ο · 0 CO β Ο 1 Ο · Ο 'Ο β Ο β Ο βΟ <βιη β ιη β ιη β ο βω -wo -η cm c cm fi cm fi cm <n -h cm cm

Ph ή Η -Η ή -Η τ-ι Ή ή -H S'- »g'-t-rl'H'H'H-rJ'-) E ^ S'-1 S'14 eesss'n ε ε ε _ __ _ Τ-. · Η -Γ-Ι τη -W Ο τι Ο τι τ-ι τι τι Ο -η Ο -π Ο τ-ι C Ή Ο · Η Ο -Η Ο -Η Ο Δ Γ0-Η τ-ι "4 O -rj Ο τ | Ο "4 '-' • Η τκ-rt τ-) · Η cn Λ rn Λ and Λ ιο Λ ιο Λ \ X) ^ Λ ^ Λ ^ Λ \ Λ V. Λ \ Λ

"β'υ" β U 'cu C U "β U OU fiU C U fi Ο BU β U β U fi U

• 5oU -Η0 "40 · τ (0 · —10 0) 0" 40 -PO · Η0 -Ρ0 -Η 0 TjO

β in Β in g in Sin Ε m tn in Bin Sin E in Sjn Ejn E in 6 n

(N CM CM CM CM CM CM CM CM CM CM CM CM CM

ooooooooooooo m -n rn -r-> mn η n rn m rn τη m -m rn m rn τη rn m rn τη rn in m τη ΛΛΛΛΛΛΛΛΛΛΛΛΛ

Br-l p p p P P P P P

H § © 0 0 O 0 O O O O

0 0Λ! β> Ό>> Ϊ1 ij ij ij ft M, ¾ τί rt βΗΗΗΗΗΗΗ 0 r 5 +) Ή 0 · Η · Η · Η · Η · Η · Ητ4

, ¾ ο β NO'NNNNNNN

lomtammmmntnmatoa ια <αιοΐΰΐΰ «οαΛΛ« 3ΐοιαΛ

r4r4r4r4r4r4Hr4r4r4Hr4H

O 'O' O 'O' O 'O' O 'O' O 'O' 0 '0' D1 800 24 23 xx «5 δ 1 2« x K x_ x „x_ 1 3 W +> 3> £ XK ) Λ 0 J3 «Λ 0 'a' ^ 'tj' ^ irr'n'CMCMCMCMrnrnfn 19 - O - - oooo OOO o

oo ^^ moocmooocm III H Η Η I I [J

I I 'f vo .. .....} I i «» rt Η H rt 1 I · 1 I I M o rt-nCrtrtiCHHHrtjei'rtrt Ό

G'O

Ai X gg • n i-ι Ai, g nin # £ «CCC -Ö j-rjmmrQwO-PfljeJejg S §§Ig« 4Jome) e> «o Ο & δ'-Ρ + 'Ο' ^ οΐ'Η> 3 D» mc (1) Ti 4h

£ U U O U Λ U 1H U U U U U U U 'O

• O 10 10 10 0 Λ0 O 0 10 j0_ 10 O c

£ Q CO CO CO CO 1 O O 1 O O CO CO CO -O 1H

5 ° -5 ° -H CN -ACM CO · O CO · O -HO -HO -HO CO £ de «η ëh ε ^ .g - <3 ε E ε ε ίί 1 2ί? 2” 2ί? 25ο ε Ο V ε £ 8 S ° '-H ° Ο 5 1 ^' ν. Λ \ Λ Λ \ Λ νο ο ΓΟΛ ΟΛ \ Λ \ Λ «CU CUCUC Ο · U Μ) · UU CU CU CU · u ^ ιλγ un i-lO« HO CO CO CO · 0 1H0 ΉΟ 1H0 CO} j {E1lo gmgm gin · πιη · ηιλ Min Clo gin gin £ 1c S irt CCN CN OJ OJ gCN g <NE <N -W CN ^ (N q NQ ™ E ™ 10 ^ «^ • οΜ-ηη-ο ^ -οίη-οιη -η τ-ίΜ ^ ο-τ, m-rn in -ri g 0 mJ t4 · Α Ή 1rf -HCN-H · Η Ή -Η «U,.

ΛΛΛΛΛΛΛΛΛΛΛΛΦ-C

• Η II c § s +> Ή Ιί Η

Ij Vi Vi n Μ »> 4 M Vc V; Vi Vi C "gw% l t l% t l I I I> I ftlt T4NNNNNNNNN N N« »g £ H Cl 3 cd c

- VI

C - Λ 0 VI 0) 4J 3 C> 01 c 01 0) CD CD CD CD CD CD CD W “g 9 N g

IBβ IB (Ö IÖ ιβ <0 10 C <0 C YyYy 1 ^ cjS

. H.-1 H rH H --1 'd' rf, uSrt

Oi CD CD CP CD CD CD CD CD CD CD CD U <j) H

<CD rt) 800 2 4 23 1 ill *> 0 101>, Η I 1θ -I 2 1 1 er) fo -ή- I /, \ q r- oo cd «-Ι” «· 1« 1 · 20 c <11> φ Η Λ α> σ »ό ό

C C C

0) 0) 0) + J Ν Ν

S S S

ϋ <0 <0 Φ U I Η Η 0) I θ> θ 'Μ> I \ ^ • η γΗ Ό Ό Ή Ή <0 <0 r-i Ν r-l »” <Η Cr> Cr> α> ρ • Η

D

3 Η> η

Μ C

φ Φ> Ρ Η Β • Η θ '

Ν C

• Η φ Ό • η ο ω m η Ρ νο <0 Λ! q Φ Φ Λ Ο Ρ Ρ φ φ α Κ ’Ο

Id C.

S <fP ο g ^ ϊ Η -Η Ν Ρ φ • Ö Λ Η <0 X _ -ο <0 Ό Ό · Η U-ι Ό θ> θ 'Λ Φ Η Φ Φ

θ 'φ Φ Φ CU

V »<8 Η> - <0 • Ö Ρ <0 Μ (jt φ φ φ Ό Φ θ 'Φ1 θ' Φ Φ Μ Η Ρ (0 Φ η Ο Φ Ή Η Μ Φ> Φ

• W

<Λ Φ Λ Ό H <Φ Ρ (0 (0 Ο Ο § Σ 800 2 4 23

Claims (8)

0 CO NCLUSIONS Method for forming an adhering metal surface on a substrate, characterized in that (I) a solid substrate is treated with at least one organofunctional silane or a partial hydrolyzate thereof, of the general formula 1, or a mixture of such an organofunctional silan or a partial hydrolyzate thereof with a second silan or a partial hydrolyzate thereof of the general formula II, in which formulas R represents an alkyl radical with 1 to 4 carbon atoms, R 'represents a difunctional hydrocarbon radical with 1 -12 carbon atoms or a radical of the formula III, x 15 represents an amino group, a radical of the formula 4, a mercapto group, hydroxyl group or chlorine, R "represents a phenyl radical or an alkyl radical of 1-4 carbon atoms and a and b are each 2 or 3, c is 0 or 1 and a + c is 3, (II) dries the silan treated surface until most of the volatiles are removed and then (III) on the On the treated surface, a metal deposit forms to form a thin continuous film or coating. 2. A method of forming an adhering metal surface on a substrate, characterized in that (I) a solid substrate is treated with a curable, organic or silicone undercoat and this undercoat hardens, (II) the cured undercoat with at least an organofunctional silan or a partial hydrolyzate thereof of the general formula 1 or a mixture of such an organofunctional silan or a partial hydrolyzate 800 2 4 23 V f thereof with a second silan or a partial hydrolyzate thereof of the general formula 2, in which formulas R represents an alkyl radical of 1-4 carbon atoms, R 'represents a difunctional hydrocarbon radical of 1-12 carbon atoms or a radical of formula 3, X represents an amino group, a radical of formula 4, a mercapto group, hydroxyl group or chlorine R 1 represents a phenyl radical or an alkyl radical 10 having 1-4 carbon atoms and a and b are each 2 or 3, c is 0 or 1 and a + c is 3 , (III) dries the silan-treated surface until most of the volatiles are removed and then (IV) deposits a metal on the silan-treated surface to form a thin continuous film or coating. A method of forming an adhering metal surface on a substrate, characterized in that a solid substrate is treated with a curable organic or silicone undercoat containing at least one organofunctional silane or a partial hydrolyzate thereof of the general formula or a mixture containing such an organofunctional silane or a partial hydrolyzate thereof with a second silane or a partial hydrolyzate thereof of the general formula 2, in which formulas R represents an alkyl radical with 1-4 carbon atoms, R 'represents a difunc-30 a hydrocarbon radical with 1-12 carbon atoms or a radical of the formula 3, X represents an amino group, a radical of the formula 4, a mercapto group, hydroxyl group or chlorine, R "represents a phenyl radical or an alkyl radical with 1-4 carbon atoms represents 800 2 4 23 and a and b are each 2 or 3 * c has a value of 0 or 1 and a + c is 3, (II) the undercoat dries until the majority 1 of the volatiles has been removed and then (III) deposits a metal on the undercoat to form a thin, continuous film or coating. Process according to claim 1, 2 or 3, 10, characterized in that the deposited metal is copper, nickel, tin, silver, silver solder, gold, aluminum, platinum, titanium, zinc or chrome. Method according to claim 1, 2 or 3, characterized in that the substrate is plastic, wood, cardboard, glass, metal, silicone rubber or silicone resin. Method according to claim 1, 2 or 3, characterized in that the substrate is in the form of a lens. Method according to claim 1, 2 or 3, characterized in that a clear top layer is also present on the deposited metal surface. 8. Object obtained according to the method of any one of the preceding claims. 800 2 4 23 (R0) a Si r'x (R0) ^ SiR4.b - ΟΗ ^ Η ^ ΟΙ-Ι *. NH CHeCH2 - I i 2 3 - NH CHj. — Cl (CHjO)} Si (CHj) 3 NHfCH ^ NHj 5 (CHjO), Si (CH ^ jNHj (CHj ^ NH CH3 CH = CH2 Cl 'W 6 (CH3oJ Si) (CH ^ SH 7 (CHjO) j Si (CHi) 4 Cl 8 (CH30), Si (CHj) 3 OH g CHj / CHsO) 2 Si (CH £) 5 NH (CHj ^ NHz] Q CHi ^ HjO) ^ Si (CHj) j NH! (CHi) 4 NH CHa ^ 3 CH; = r CHj Cl> »11 CHj (CHiO) i Si (CHjl SH 12 CHj (ch3o) j Si (CHj Cl 13 CHj (CH3O, Si (CH5) 3 OH-phenylSi (OCH) propylSifOCH), CH = CHS; (OCH) 15 16 17 800 2 4 23 CH 2 -tOCH 18 DOW CORNING CORPORATION, of Midland, Michigan. America