CA1197417A - Protected vapor-deposited metal layers - Google Patents

Abstract

Abstract of the Disclosure The use of organic materials containing carbonyl groups, phenoxy groups, ester groups, polysaccharides, phthalccyanine, or alcohol groups over vapor deposited metal layers improves their mar resistance. These organic materials can improve the properties of the metal layer when used in photoresist imaging films.

Description

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PROTECI'E~ VAPOR-DEPOSITED METAL LAYERS
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BACKGROUND OF THE INVENTION
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Field of the Invention This invention relates to vapor~deposited metal layers which are protected from damage by the application of an o-~ganic layer to its sur~ace. The invention further relates to the process of applying tlle protective organic layer to the surface of the vapor-deposited metal layer and to the photosensi~ive articles made with the protected metal layer.
In particular, the presen-t invention relat~s to the application of an organic layer onto the surEace of a vapor deposited metal layer~ The metal layer is generally formed on a supporting base hy any of t~e various vapor~
depositing techniques. Prior ko subjecting the deposi~ed metal layer to any physical treatments or stress likely to damage the continuity of the coating (e.g., rolling, folding, bending, and the like~ an organic layer is vapor deposited onto the surface of the metal.

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Vapor-deposited layers of metals, particularly those on flexible webs~ tend to be soft an~ easily rubbed off. These defects are particularly unacceptable where such layers are to be used as part of an imaging system consistin~ oE a vapor deposited metal layer and an over-coated photoresist or photopolymer layer. Marks, scuffs, kinks, or abrasions in the metal layer produce voids or areas in the ~ilm which contain no useful image, thus interrupting the ~aithfulness of the imageO These photographic defective areas have been called ~y various names such as pinholes, cinch marks, scuffs, etc., dependlng on where and how the abrasion was produced. In order to avoid such de~ects~ a protective resin layer is generally coated on the metal layer. This is often done in a seE)arate coating operation on a di~ferent coatin~
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2-machine. The difficulty with this practice, however, is that ~he unproteeted vapor-coated metal film rnust be wound after the vapor--coating operation to transport -the material to the more conventional resin coater. Defeets sueh as cinch marks, abrasions, and kinks are of~en produced during this winding operation.
In order to avoid the problems deseribed above~
several attempts have been made to vapor-deposi~e the metallic and organic layers in the same vacuum chamber, thus eliminating the need to wincl the film in a roll between eoatin~ operationsO One such proeess is deseribed in UOS~ 4~26S,541. Here the vapor-deposition chamber is divided into 2 sections, by means of a par~ition, thereby separating the metal deposition area from the organic lS deposition section. Thus the organic protective layer is deposited over the metal layer without the need to rewind the roll in between the two eoating operations~
The organic compounds used in U.S PatO 4,268,541 include polymers (for example, those derived from meth-acrylic aeid and acrylie aeid), low molecular weightorganie compounds containing a carboxyl group ~e~
compounds such as abietic acid, isophthalie aeid/ behenic aci~, terephthalic acid, phthalic acid, etc., and a few randoM compounds (e.g., Rhodamine B, rosin, a phthalo-cyanine, a monosaccharide/ and an oligosaccharide).
l'he technique and materials described in U.S.4,~68~541 have been founcl to be suitable for only limited uses. The layer thickness of 30-60~ nm specified with those materials disclosed is not suitable for many imaging film constructions, and for many procc-ssing teehniques. In ~articular, the riction properties of the coating cause layers of the coated Inaterial whieh are stac~ed or rolled to slide and move out of register. In rolled form~ tele seoping of the roll is quite serious. This can cause serious delays and expense in further use of the film.
Organic protection layers located between the metal layer and a photoresist layer can clrastically a~fec-t '7 --3~
the oxidi~incJ or etching step and the quality of the resulting image, For, example, excessive thic.kness of such layers may provide a preferential pathway for the developer or etch solution thereby resulting in image degradation or fine detail loss. This is especially true of material whose final designation is copy or contact reprographic work. Films such ~s these, called li.th or contact films, depend on fine dot arrays to reproduce image tone Fine dots (3-5%~ may be undercut and etched away thereby degrading the quality of the reproduction.
The relatively thick layer oE some acid-con-taining protective materials such as disclosed in U. S~ Pat~
No. 4,2Ç8,541 can also interfere with the etching of the metal hy neutralizing -the alkaline metal etching solution.
Such neutralization inhibits the formation of an etched metal in~age and thus interferes with the formation of an image of acceptable qualityO
Another attempt at o~ercoming the abrasion problems is described in Japanese patent publication number 56/9736. In this case, the metal and the oryanic compound are deliberately coated as a single layer; i.e., the metal and organic vapors are substantially lnixed in the vapor stream before they are deposited on the supportO ~his is not completely satisfactory because the heated metal vapor can carbonize or decompose the organic material resulting in an unacceptable productL ~lso, the thickness of the layer is required to be at least 2n to 1000 mm~ The scope of organic ma-terials is also quite specific and generally emphasizes organic acid materials.

SUMMARY OF THE INVF.NTION
The application of layers of organic material with a vapor pressure at 20C no yreater than l-n-octanol said material having 1) carbonyl groups which are not part of carboxyl groups, 2) phenoxy yroups, 3) ester groups, 4~ ~rea groups, or 5~ alcohol groups onto vapor~deposited metal surfaces has been ~ound to provide excellent damage resistance to the metal layer as coatlnys of 1 to 600 nm. Organic materials having 1) carboxyl groups, 2) polysaccharides, 33 Rhoda--mine B, and 4) phthalocyanines provide excellent resistance in thick-ness of 1 to less than 30 nm. The presence of these organic mate-rials ~n he vapor-deposlted metal layer in photoresist imaging constructions provides for uni~orm development characteristics in the image. These materials reduce or eliminate the low friction properties attendant with -the use of acids as protective layers, and because of reduced acidlty these materials do not neutralize alka-line developing solutions as much as acid protective layers.

DETAILED DESCRIPTION OE' THE INVENTION

, The basic article of the present invention comprises a substrateJ a vapor-deposited metal layer on at least one surface of said substrate, and a 1 to 600 nm protec-tive organic layer on said metal layer comprisin~ a material having phenoxy groups, alcohol groups~ urea groups, ester groups, or carbonyl groups which are not part of carboxyl groups or a 1 tc less than 30 nm organic layer oE
a 1) carboxyl containing~ compound 2) polysaccharide, 3) Rhodamine s or 4) phthalocyanine. In a pre-Ferred embodiment, a photoresist layer ls coated over said protective layer.
The substrate may be any surface or material onto which metal may be vapor-deposited. The substrate may be rough or smooth, transparent or opaque, and continuous or porous~ It may be of natural or synthetic polymeric resin (thermoplastic or thermoset), ceramic, glass, metal, paper, fabric, and the like. For most commercial purposes the substrate is preferably a polymeric resin such as polyester (e.g., polyethyleneterephthalate), cellulose ester, polycarbonate, polyvinyl resin (e.g~, polyvinylchloride, polyvinylidene chloride, polyvinylbutyral, polyvinylformal)~
polyamide, polyimide/ polyacrylate (e.g., copolymers and homopoly-mers of acrylic acid, methacrylic acid, n-butyl ``r~ ~ ~ 4a -acrylate, acrylic anhydride and the like), polyolefin, and the like. The polymer may be transparent~ translucent or opaque. It may ~ontain fillers such as carbon black, titania, 2inc oxide, dyes, pigments~ and of course, those materials generally used in the formation of films such as coating aids, lubricants, antioxidants, ultraviolet radiation absorbers~ surfactants, catalysts and ~he like.
The vapor-deposited metal layer may be any vapor-deposited metal or metalloid layerP According to the practice of the present invention, the terrn metal layer is defined as a layer comprising metal, metal alloys, metal salts, and metal compounds. The corresponding meaning applies to the term metalloid layer. The term metal in metal layer is defined in the present invention to inclu~e serni-metals (i.e~, metalloids) and semiconductor materials.
Metals include materials such as aluminum, antimony, beryllium, bismuth, cadmium; chromium, cobalt, copper~
gallium, germanium, gold, indium, iron9 lead, ma~nesium, manganese, molybdenum, nickel, palladium, rhodium, selenium, silicon, silver, strontium~ tellurium, tin/
titanium, tungstenr vanadium, and zinc. Preferably the metal is selectecl from aluminum, chromium, nickel, tin, titanium and zinc. More preferably the metal is aluminumJ
Metal alloys such as aluminum~iron, aluminum-silver, bismuth-tin, and iron-cobalt alloys are included in the term metal layer and are particularly useful. Metal salts such as metal halides, metal carbonates, metal nitrates and the like are useflll. Metal compounds such as metal oxides and metal sulfides are of particular utility in imaging systems. Metal layers comprising mixtures of these materials such as mixtures of metal-metal oxides, rnetal-metal salts, and metal salts-metal oxides are also of particular interest.
The thickness oE the vapor-deposited metal layer ~lepends upon the particular needs of the final product. In imaging constructions, for example, the thickness should be at least about 3 nm. Generally, the layer would be no thic~er than 750 nm which ~ould req~ire a long etching period. A more practical commercial range would be between 10 and 500 nm. A preferred range would be between 20 and 400 nm and a more preferred range would be between 25 and 300 nm or 30 and 20Q nm.
It is preferred that the majority of the cross-section of the metal layer consist essen-tlally of metal t metal alloys~ metal salts and metal compounds~ Traces of up to 13% or more of other materials may be tolerated generally in the layer, and in fact in certain ~rocesses of manufacture ~he boundary region of the metal layer and the protective layer may have a graded or gradual change from 100~ metal to 100% organic material. But metal layers with the majority (at least 50~ of its cross-section consisting essentially of metals, metal alloys, metal salts, metal com-pounds and combinations thereof are preferre1. The metal layer should have fewer than ]00~ preferably fewer than 50, and more pre~erably fewer than 30 defects per 177 rnm2 Vapor-deposition of the metal layer may be accomplished by any means~ Thermal evaporation of the metal, ion plating) radio frequency sputtering, A.C.
sput-tering, D.C. sputtering and other known processes for depo~sition may be used in the practice o~ the present invention. Ilhe pressure may vary greatly during coatiny, but is usually in th~ range of l~-fi to 10-4 torr~
The organic protective layer which may be from 1 to 750 mn comprises a material with a vapor pressure at 20C no greater than that o~ l-n-octanol selected from the group consisting of 1) organic materials having carbonyl groups which are not part of carboxyl groups, 2) phenoxy groups, or 3) alcohols. The tenn "organic rnaterial" is used because the protective coating does not have to be a single compound or a monomeric compound. In addition to those types oE materials~ dimers, trimers, oligomers, polymers, copolymers, terpolymers and the like may be used.
The organic materials containin~ carbonyl groups which are not part of a carboxyl group, ~or example, i ~ ~ 7 ~1 J
-~7 include 1) amides, such as phthalamide, salicylamide, urea formaldehyde resins, and methylene~bis-acrylamide, and 2) anilides, such as phthalanilide and salicylanilide. It has been found that these organic materials may be used in layers as thin as 1 nin and provicle good abrasion or mar protection. They may be used in thicknesses of up to 600 nm, hut without dramatic improvement of results, and in fact often with some diminution of properties. A preferred range would be between 3 and 200 nrn, more preferably between 5 and 100 nm, and most preferably at least 5 and lower than 30 or 20 nm.
The organic material containing ester groups includes such materials as polyester oligome~fs, low Inolecular wei~ht polyester polymers (e.g., polyethylene terephthalate, polyethyl2neisophthalate, etcO having molecular weight.s between 5,0~0 and 50,000)~ diallyl phthalate (and its polymers), diallyl isophthalate (and its polymers) 9 monomethyl phthalate, carboxylic acid alkyl esters, and the likeO
The ort~anic material containing phenoxy groups include such materials as Bisphenol A, and low molecular weight ~henol formalt~ehyde resins (e.g., Resinox~)~ The alcohol containing materials would include l-n~octanol, ~o~ecanol, benzyl alcohol and the like.
The organic protective layer comprises a material selected from the group consisting oE or~anic materials having 1) carboxyl groups, 2) saccharide, or 3~ phthalo-cyanine. Preferably these rnaterials have a vapor pressure at 20C which is not higher than -that of 1-n~octanol. The term "organic material" is used because the protective coating does not have to be a single compouncl or a mono-meric compound. In addition to those types oE materials, dimers, trimers, oligomers~ polymers, copolymers, ter-polymers and the like may be used.
The organic materials containing a carboxyl group, for example~ include aliphatic carboxylic acids, aromatic carboxylic acicls, acrylates~ polyacrylates, 7~

copolyacrylates~ polycarboxylic acids and the like as described in U~So Patent 4,268,541.
The organic material should be vapor-depositable as thi~ is the general method preferred for applicakion of the protective layerO The organic material may, for example, be deposited in the apparatus and procedures disclosed in U.S. Patent No. 4,268,~41. The partition or baffle described in that apparatus (e.g., Example 1) has not been found to be essential. The two vapor streams ~iOe., ~etal and organi~ material s~reams) may be physically spaced apart or directed 50 that the coating zones for the two ma~erials do not completely overlap. No serious problem has been found even when 50~ of each of the coating zones overlap (so that at least 50~ of the thick-ness of the metal layer consists essen-tially of metal, metal salts, metal compounds, and combinations thereof), although this is not a preferred construction. It is preferred that less than 25~ of the total weight of the metal component he in such an overlapping or mixing zone and more preferably less than 10~ or even 0~ be in such zones. The recitation of a metal layer in the practice of the present invention re~uires, however, that at least a region of the coating, usually adjacen~ to the substrate~
consists essentially of a meta] layer without a dispersed ~hase of organic material therein.
The photoresist layer may be either a ne~ative-acting or positive acting photoresist as known in the ac-t.
Positive acting photoresist systems ordinarily comprise polymeric binders containing positive acting diazonium salts or resins such as those disclosed, for example, in U.~. PatentS Nos. 3,046,120, 3,469,~02 and 3,210,239. l'he positive acting pho~osensitizers are commercially available and are well reported in the literature. Negative acting photosensitive resist systems ordinarily comprise a poly-merizable composition which polymerizes in an imagewisefashion when irradiated, such as by exposure to light.
These compositions are well repor-ted in the literature and are widely comlnercially available. I~hese compositions ordinarily comprise ethylenically or polyethylenically unsaturated photopolymerizable materials/ although photo-sensitive epoxy systems are also known in the art.
Preferably ethylenically unsaturated photopolymerizable systems are used, such as acrylate, methacrylate, acrylamide and allyl systems~ Acrylic and methacrylic polymerizable systems are most preerred according to the practice of the present invention. V S. Patents Nos.

3,639,185, 4,~7,616~ 4,008,084, 4,138,~62, 4,139t391,

4,158,079, 3,46~,982, U.K. Patent No. 1,468,746, disclose photosensitive compositions generally useful in the practice of the present invention. U. S. Paten~ NOD
4,314,022 discloses etchan-t solutions particularly useful in the practice of the present invention.
The followiny examples f~rther illustrate prac-tice of the present invention~

Example 1 Usin~ the apparatus described in U.S. Patent NoO
4,268~541 without a baffle, a 10~4m polyester web was coated by vacuum ~eposition with 70nm of aluminum. ~uring the same operation in the same vacuum chamber a layer of a commercially available terpolymeric acrylate material (derived from 62~ methy:Lmethacrylate, 36% n~butylacrylate and 2% acrylic acid by weight) was applied. This sample represents an article made accordiny to the teachings o~
U.S. Patent 4,268,541. A control length of non organic-coated aluminum film was also produced. Ellipsometric measurements of the resultant organic/metal package indicated that the thickness oE the acrylate layer was 30O5nm.
The resultant aluminum plus organic coated material was examined by way of transmitted lic3ht and exhibited ~ery few pinholes or defects. The otherwise soft aluminum layer of this package could not be ru~bed off using thumb pressure. The non organic coated aluminum film could be rubbed oEf using thumb pressure~
Both the organic vapor coated sample and the unprotected sample were immersed in a bath of 1.2~ sodium hydrox:de and 3~ of the tetra sodium salt of ni~rilo triacetic acid at 32C. The unprotected Al layer was uniformly~ cleanily oxidized away in 15 seconds~ The organic-protected layer was not cleanly removed. In fact, the aluminum ]ifted off in sections during the immersion time and then the aluminum generally oxidized in solution.

Example 2 .

Usin~3 the apparatus described in the Example 1, a 2000 meter continuous web was vapor coated with a 70nm layer of aluminum and immediately thereafter in the same chamber, a 10 nm layer of terephthalic acid was applied.
At the 1400 meter level, the terephthalic coated roll telescoped on itself and telescoped furtller when removed from the chamber. After removal from the chamber, the vapor-coated aluminum/terephthalic acid roll was judged to be unacceptable for produc~ion purposes~

Example 3 Using the technique c]escribed in Example 1/ three more rolls of 2000 meters were coated and a diferent organic`material applied to the alumin~ of each of these rollsO Roll A contained an organic layer (on top of the aluminum layer) consisting of Resinox~ a phenol formaldehyde condensate resin made by the Monsanto CorpO
Roll B was identical to Roll A except than an organic layer of ~itel 200, a low molecular weight 30 polyester resin lapproximately 10~000 molecular weight) made by and commercially available from Goodyear was applied to the aluminum layerO Roll r consisted of a control roll of vapor-coated aluminum film identical to ~4-r~e ~

7~
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rolls ~. and B with no organic protec~ive coati.ngO
None of these three rolls telescoped.

Example 4 =. ~ ~_ Using the apparatus of Example l, ~he following materials were applied to vapor-coaked aluminum webs in various thick nesses from 15 to 250 nm.
l) Dimethyl terephthalate 2) Phthalic anhydride 3~ Mono methyl phthalate O 4) Dapon 35 - a diallyl phthalate prepolymer made by FMC
Corp.

5) Bisphenol A

6) Epon 828 - an epoxy resin made by the Shell Corp.
73 Michlers Ketone ~) Benzophenone 9) ~enzyl alcohol lO) Salacylamide These materials were unrolled after coating an~ .inspected with a lOX hand lens by transmitted light. 'he defects ln an area of 177mm~ were counted and compared -to those of a non organic coated aluminum film prepared as a control.
'I'he control film exhi~ited defect levels over lO0. The materials tested had defect levels of 30 or less. ~he control material that had no protective layer could be rubbed oif using thumb pressure - the organic protecti.ve material could not, None of the above materials felt sl.ippery and none produced any telescoping during or ater rolling.

Example 5 Usiny the apparatus of Exalnple l~ two coatings were made on top of a 70nm aluminum layer, one using a protective coating of Resinox as the organic layer; another using terepllthalic acid as the organic layer. Both these organic layers were applied to produce an organic layer of about 5nm thickness as determined by a Gaertner Ellipsometer.
These two webs were further coated with a resis-t layer of the type described in our copending Canadian applica-tion Serial No. 420,095 Eiled on January 24, 1983. A control web consisting of only the 70 nm aluminum layer was prepared as well.
After coating and drying these films were exposed to a 10 step Stauffer grey scale using a 2kw Berkey Ascor printing source (light to film distance 1 mtr) for 15 seconds. The exposed films were developed in the processing solution described in Example 1 of United States Patent No. 4,314 t 022 Eor 30 sec, at 38C followed by a warm water wash. On inspection it was evident that the Resinox and control film had grey scale values of step 5, the terephthalic acid roll however had a grey scale value of 7 indicating a faster, more uncontrolled development.
xample 6 Using the technique of Example 1, a Vitel 200 polyester coating was applied in a thickness of 10 nm to various metal layers including 1) Tin 2) Copper 3) Aluminum/Mg (Al 94.8%; Mg 5.0~; Mn 0.1~; Cr. 0.1~) 4) Aluminum plus Iron (ratio A12Fe5) 5) Nickel A control non-organic coated layer was included for each metal while thumb action rubbing was able to rernove -the unprotected metal. The protected metal layers (organic coated) would not rub off.

~ 9 ~ ~ ~t~

Example 7 Using the technique described in Example 1, 4 separate, 30 me-ter, 10~4m polyester base samples were continuously vapor-coated with aluminum (thickness 70nm). One of these was additionally vapor-coated (in the same pass time and vacuum chamber as the Al layer) with a 30nm layer oE a 62/36/2 methylmethacrylate/n~butylacry]ate/acrylic acid terpolymer (henceforth called Sample A). The second web was additionally vapor-coated with a 30nm layer of tereph-thalic acid (in the same pass time and vacuum chamber as the aluminum layer - henceforth called Sample B). The 3rd sample called C was made identical to Sample B but the thickness of terephthalic acid was reduced to 10nm. The 4th sample (D) was not overcoated with an organic protective layer. All of the above webs were wound up in vacuum under a tension equal to 40 lbs.
Sections of all of the samples were unrolled and viewed on a graphic light source and inspected using a 10X hand magnifying glass. Scratches, cinch marks, and other deEects were counted on different areas of each web.
Selec-t areas of 177mm2 were viewed and the defects counted. Table l list the defect levels of each web~
TABLE l SAMPLE DEFECT LEVEL

All of the above webs were coated wi-th -the photoresist of Example 3 of Canadian Serial No. 420,095 filed on January 24, 1983 at a coating weiyh-t of 231 my/ft2. After coating, each of these samples was exposed to a 10 step Stauffer grey scale usiny a Berkey Ascor 2kw commercial liyht source (larnp to film ~istance 1 , ~ -13a-~, ~

1~-meter) using a metal halide lamp for a period oE 15 seconds~ After exposure, these films were developed in a Graphic Arts rapid access processor. Processing conditions include a 60 second development time using the developer S solution of Example 1 of U.S~ Patent No 4~314rO22 at 39~C
followed by a 30 seond wash cycleu The 10 step grey scale reproductions on each o these films was examined. Table 2 details these re 5 ul ts.

__ SAMPLE STEPS SEEN CO~IMENTS
A 2 Large areas removed non i/nagewise B 7 3-5~ dots undercut C 4 Good sharp 3% dots D 4 Equal dots to Sample C

These data clearlv indicate that the h.igher coatin~3 levels o:E organic protective material taught in rJ~s~ Patent 4,268,541 interfere with development, producing inferior reproductions, although they adequately prctect the A1 web from defects.

Example 8 -Using the technique described in Example 1, eighk separate, 30m polyester base samples were continuously vapor-coated with different metals of nominally the same thickness as in Example 1. One .sample of each of the followin~ metal layers was overcoa-ted with a protective layer.

Tin 2 Coppe r 3 Aluminum 4 Alumirlwn/Magnesium ~Al 94.8%; Mg 5.0~;
Mn 0.1~; Cr 0.1%) S Al~Fe5 The protected layer f ilms had a 8nm layer oE terephthalic acid vapor~coated on top of the metal layer~ At the same time, the metal layer was vapor-coated in the same pass and vacuum chamber. A 10X inspection of a 177mM2 area of each of the webs placed over a li~hted table indicated the following defect levels.

DEFECT COUNTS/177mm~ AREA
METALPROTECTED LAYER UNPROTECTED LAYER
Tin 19 170 Copper 22 163 Aluminum 18 135 Aluminum/Ma~nesium 20 142 Aluminum/Iron 19 150 Example 9 Usinl3 the technique of Example 1 several diEferent materials were in-line, in situ vapor-coated on top of a 70nm layer of aluminum at the time the aluminum layer was applied~ These were applied in 2 levels a level of 8nm and a level of 30nm and wound up in a roll from under a take-up roll tension of 40 pounds.
1) Terephthalic acid 2) Salicylic ac id 3) ~rerpolymer of 62% by wei~ht methyl rnethacrylate, 36%
n-butylacrylate, and 2~ acrylic acid ~) Behenic acid -16~
After application, each of these samples were perused with a lOX hand lens and defec~ counts conducted in areas of 177mm2. The following table details the observation of these studies as well as additional notes. The data was compared to a web coated with aluminum of the same thick-ness and at the same thickness and at the same time as the other samples.

Material Untreated Level 3nm Level 30nm ~lotes . ~
Unprotected Aluminum 1000 Terephthalic acid -~-- 20 23 30nm level;
powdery~
not optically clear;
both slippery.
Salicylic acid ---- 23 22 30nln level;
slippery;
roll telescoped.
Acryl ate Terpolymer ---- 1~ 21 removed :Erom base in chunks by developer (30nm) Behenic acid 20 23 30nm level tacky.

'7~

The above data show that the thickness range o~ 8 to less than 30nm provides excellent protection ayainst ahrasion defects but that the thicker layer tends to create other difficulties such as reduced optical clarity, excessive slipperiness and tackiness.

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1 A process for improving the abrasion resistance of vapor deposited metal layers which comprises vapor depositing a metal layer on at least one surface of a substrate and, before sub-jecting the metal layer to physical treatment or contact which would abrade the metal layer, vapor depositing onto said metal layer 1) a 1 to 600 nm layer of organic material having a vapor pressure at 20°C equal to or less than that of 1-n-octanol said material having a) a carbonyl group not part of a carboxyl group, b) a phenoxy group, c) an ester group, d) a urea group, or e) an alcohol group, or 2) a layer of organic material having a thick-ness of at least 1 nm and less than 30 nm and a) a carboxyl group, b) a saccharide, c) Rhodamine B, or d) phthalocyanine.

2. The process of claim 1 wherein at least 75% of the thick-ness of said metal layer consists essentially of a material selected from the group consisting of metals, metal compounds, metal salts and combinations thereof.

3. The process of claim 1 wherein said metal layer consists essentially of a material selected from the group consisting of metals, metal compounds, metal salts, and combinations thereof.

4. The process of claims 1, 2, or 3 wherein said organic material is selected from the group consisting of amides, anilides bisphenol A, phenol formaldehyde resins, low molecular weight polyesters, and alcohols having a vapor pressure at 20°C no higher than 1-n-octanol.

5. The process of claims 2 or 3 wherein said organic material is selected from the group consisting of alkyl esters of car-boxylic acids, polyester oligomers, and polyester polymers.

6. The process of claim 2 or 3 wherein said organic material is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, and acrylic or methacrylic polymers or copolymers.

7. An article comprising a substrate having on at least one surface thereof a vapor deposited metal layer and adhered to said metal layer 1) a layer of 1 to 600 nm comprising an organic material having a vapor pressure at 20°C less than or equal to that of 1-n-octanol and having a) a carbonyl group which is not part of a carboxyl group, b) a phenoxy group, c) an ester group, d) a urea group, or e) an alcohol group, or 2) a layer of organic material having a thickness of at least 1 nm and less than 30 nm and a) a carboxyl group, b) a saccharide, c) Rhodamine B, or d) phthalocyanine.

8. The article of claim 7 wherein said metal layer consists essentially of a material selected from the group consisting of metals, metal compounds, metal salts and combinations thereof.

9. The article of claim 7 or 8 wherein said organic material is selected from the group consisting of amides, anilides, bisphenol A, phenol formalde resins, polyester resins having a molecular weight between 5,000 and 50,000, and alcohols having a vapor pressure at 20°C no higher than that of 1-n-octanol.

10. The article of claim 7 or 8 wherein said organic material is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, and acrylic or methacrylic polymers or copolymers.

11. The article of claim 7 having coated over said organic material a photoresist layer.

12. The article of claim 7 or 8 wherein said organic material is selected from the group consisting of amides, anilides, bisphenol A, phenol formalde resins, polyester resins having a molecular weight between 5,000 and 50,000, and alcohols having a vapor pressure at 20°C no higher than that of 1-n-octanol and having coated over said organic material a photo-resist layer.

13. The article of claim 7 or 8 wherein said organic material is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, and acrylic or methacrylic polymers or copolymers and having coated over said organic material a photoresist layer.