CA1229265A - Method of providing a metal mirror - Google Patents
Method of providing a metal mirrorInfo
- Publication number
- CA1229265A CA1229265A CA000468452A CA468452A CA1229265A CA 1229265 A CA1229265 A CA 1229265A CA 000468452 A CA000468452 A CA 000468452A CA 468452 A CA468452 A CA 468452A CA 1229265 A CA1229265 A CA 1229265A
- Authority
- CA
- Canada
- Prior art keywords
- synthetic resin
- metal mirror
- treated
- tannic acid
- metallization process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
ABSTRACT:
"Method of providing a metal mirror".
A method of providing a metal mirror on a synthetic resin surface in which the surface of a syn-thetic resin which comprises a carboxylic acid amide group is pretreated with tannic acid and the surface of a synthetic resin which is a polyester, a polyolefine or a polyolefine containing halogen atom(s) or aromatic group(s) as substituents, is subjected to an oxidizing treatment and is then treated with tannic acid and the treated surface is provided with a metal mirror by means of an electroless metallization process.
"Method of providing a metal mirror".
A method of providing a metal mirror on a synthetic resin surface in which the surface of a syn-thetic resin which comprises a carboxylic acid amide group is pretreated with tannic acid and the surface of a synthetic resin which is a polyester, a polyolefine or a polyolefine containing halogen atom(s) or aromatic group(s) as substituents, is subjected to an oxidizing treatment and is then treated with tannic acid and the treated surface is provided with a metal mirror by means of an electroless metallization process.
Description
PUN. 10.849 The invention relates to a method of providing a metal mirror on an article of which at least the sun-face on which the metal mirror is to be provided is menu-lectured from a synthetic resin.
A suitable method of providing a metal mirror on a substrate of a synthetic resin is known from Tech-Nikolai Proceedings of the sty Annual Convention of the American Electroplates' Society, June 14-18, St. Louis, 1964, I. 139-149. According to this known process, an aqueous metal salt solution and a solution of a reducing agent are simultaneously atomized (sprayed) onto the sun-face to be metal plated In metal-plating synthetic resins, the comparatively low polar of polar surface must first be pretreated chemically or mechanically and then be sensitized with a reducing agent, for example Snuck. In Table 2 on page 140 of the above-mentioned literature reference, various chemical pretreatment agents for sync Thetis resins are recorded.
United States Patent Specification 3,094,430 states that upon silver-plating acrylic plastics, the surface is pretreated with a solution of tannin acid. A
sensitizing treatment with Snuck is not used. Export-mounts have demonstrated that a silver mirror provided in this manner on an acrylate synthetic resin or a Matthew-cruelty synthetic resin shows an insufficient adhesion.
It is lcnown from Canadian Patent 1,192,098 -issued August 20, 1985 (PUN 10.106) in -the name of Applicants to polymerize a polymerisable monomer compost-lion which comprises monomeric acrylates and an N-substituted pyrolidone compound, to -treat the resulting synthetic resin surface with, for example, tannin acid, and then to provide a metal mirror by means of a metal-plating process.
:
-~2~9~65 PUN OWE -2- 17.2.1~4 The treatment of an acrylic plastic White -tannin acid known from the above mentioned United States Pa-te1Lt Specification has -the disadvantage that an adhererL-t silver mirror cannot be obtained. The treatment with -tannin acid known from the above-mentioned Netherlands Patent Apply-cation has the disadvantage that it can be applied only to a special synthetic resin, namely an acrylate synthetic resin which comprises an Substituted pyrolidone compound In the preparation of this special synthetic resin the pyrolidone compound is not completely copolymerized. The remaining pyrolidone molecules are volatile and in the course of time can adversely influence the quality of the provided metal mirror.
It is the object of the invention to provide a method which does not exhibit the above-mentioned dozed-vantages.
According to the invention this object is achieve achieved by means of a method of the type mentioned in the opening paragraph which is characterized in that the surface of a synthetic resin which comprises a carboxylic acid aside group is treated with tannin acid and is then provided with a metal mirror by means of an elec-troless metallization process, and that the surface of a synthetic resin which is a polyester, a polyolefine or a polyolefine containing halogen atom(s) or aromatic group(s) as subset-tents is subjected to an oxidizing -treatment, is -then treated with tannin acid, and is furthermore provided with a metal mirror by means of an electroless me-talliza-tion process.
The invention is based on the recognition trained by Applicants -that a pretreatment with tannin acid, in particular in combination with an oxidizing pretreatment step, has a more universal character and can be applied to the above-mentioned types of synthetic resin, in which after metallisa-tion, a very adherent metal mirror is ox-twined. Tile metal mirror also remains bonded to the sync Thetis resin sL1rLace after ageirlg tests, for employ a cyclic moisture test.
I
Ply 10.~L~9 -3- 1'7.2.198L~
In a favorably embodiment, a Sirius Or pull-imide, polyamide, polyurethane or pull re-tha1-e)acrylate which all comprise a carboxy~Lic acid aside group ( I ), is treated with -tannin acid, which -treatment may be pro-ceded by an oxidizing treatment and -then provided with a metal mirror by using an electroless metalliza-tion process.
I-n a further ~avourable embodiment a surface owe polyethylene, polyvinyl chloride, polystyrene polyethylene tereph-tha:Late~ polyacrylate or polymethyLmethacrylate is subjected to a corona discharge, is -treated with -tannin acid, and is provided with a metal mirror by means of an electroless metallization process.
corona discharge is a known process in which a high voltage is applied between the synthetic resin sun-face and an electrode. As a result of electric discharge, high-energy particles will be formed, for example atomic oxygen, electrons :iOI19 and the like which impact against -the synthetic resin surface, the composition oath sync Thetis resin at -the surface varying and in particle oxygen being bound -to -the surface of the synthetic resin.
The synthetic resin surface is oxidized and obtains a hydrophilic character.
In anther favorably embodiment of -the method in accordance with -the invention a Sirius of polyvinyl chloride or po:Lycar'bonate is -treated with chronic acid, -then with tannin acid, and is provided Wyeth a metal mirror 'by means of an e:Lec-troless rnetalliza-tion process.
The invention -will be described in greater detail with refererlce to the oiling example.
Example The surface of' a synthetic resin as recorded ill colui1ln -I of -the Table below is su'bJectecl ['Or a Lowe seconds to a coronae discharge by mccrls of a IF gerlerator having a sinusoidal alternating -voltage of TV and a t`reclllellcy ox 20-L~0 clue wt1icLl is conrlccl Clue Lo an electrical placed above the surface of the synthetic resin. The surface Ott tile syntilet-ic resin is then tLeate(:l Witty all aqueous Sue lion of tanrl:ic azalea rotor at most ore Malta a-t a tunneler-s PIN l0.~49 -4- 17-2-198~1 lure of I C. The concentration owe -tannin acid in the solution is no-t restricted -to narrow limits and may 'be chisel, by Jay owe example, between 0.1 and lo g ox -tannin assess per ire If desired the solution may also comprise water miscible organic solvents, or example, an organic acid, alcohol, acetone either or ester. The synthetic resin surface may be clipped in the solution ox tannin acrid. A solution ox tannin acid may also 'be sprayed or poured onto the surface to be treated.
The synthetic resins recorded in column 1 of the Table have been pretreated only with -tannin acid in a second series ox tests, no preceding oxidizing treatment being used.
after the -treatment -with -tannin acid, a metal mirror, for example an A mirror, is provided by electron less metal-plating. or -this purpose, the synthetic resin surface is treated with a sensitizing solution. In the case of providing an A layer, -the surface is treated for 1-60 seconds with a sensitizing solution which comprises an aqueous, acid Sneakily solution. The concentration of Sneakily is not restricted to narrow limits and is preferably from 0.01 to 1 g ox Sneakily per lithe, such as 0.1 g per lithe. The treatment may be carried out 'by means ox, or example, a dipping process, a pouring process or a spray-in process. The synthetic resin surface is then treated with -Thor actual me-tal-p~La-ting solutions, hence with the awakes metal salt solution, for example, an arnmoniacal silver nitrate solution no a-n aqueous reducing agent soul-Tony. on example owe` a suitable reducing agent is formal dchyde in combination with a sugar, or example sodium g'LIlconate. The meta:L-p:LatirIg solutions are preferably pro-v:idocl accorcI:ing to -the aerosol metaI-plat:irlg process in Welch tulle solutions are simultaneously slurred onto the syntIlet:ic -resin swirls. This process, as well as -tile metal salt solutions and education agent solutions used -the-reirl are described, OILY` example, in tile above-Irlet-ltioned literature roarers technical ProceediIIgs etc.". Various mutilating chemicals are commercially available frown PUN 10.S49 I l7.2.1984 for example, Messrs. Ermax, London Laboratories Lid or Merck.
The bonding of -the silver layer thus platted on the underlying synthetic resin surface is tested according to -the so-called diamond scratching -test (DIN 53151). Act cording to this standard test, twelve scratches are pro-voided in the surface of` the metal layer so as to extend over the whole width of -the metal layer. The pattern of sorts comprises 6 parallel sureties having a mutual lo distance of 1 mm which are crossed at right angles by likewise 6 parallel scratches having a mutual distance of 1 mm so that the pattern of scratches comprises 25 areas of 1 mm . An adhesive tape is pressed on the pattern of sureties and is then pulled off from -the surface. The extent of bonding is expressed in numbers 0-5, ill which :
0 = optimum bonding; 0 areas worn loose.
1 = good bonding; -l-5 areas oarlock loose
A suitable method of providing a metal mirror on a substrate of a synthetic resin is known from Tech-Nikolai Proceedings of the sty Annual Convention of the American Electroplates' Society, June 14-18, St. Louis, 1964, I. 139-149. According to this known process, an aqueous metal salt solution and a solution of a reducing agent are simultaneously atomized (sprayed) onto the sun-face to be metal plated In metal-plating synthetic resins, the comparatively low polar of polar surface must first be pretreated chemically or mechanically and then be sensitized with a reducing agent, for example Snuck. In Table 2 on page 140 of the above-mentioned literature reference, various chemical pretreatment agents for sync Thetis resins are recorded.
United States Patent Specification 3,094,430 states that upon silver-plating acrylic plastics, the surface is pretreated with a solution of tannin acid. A
sensitizing treatment with Snuck is not used. Export-mounts have demonstrated that a silver mirror provided in this manner on an acrylate synthetic resin or a Matthew-cruelty synthetic resin shows an insufficient adhesion.
It is lcnown from Canadian Patent 1,192,098 -issued August 20, 1985 (PUN 10.106) in -the name of Applicants to polymerize a polymerisable monomer compost-lion which comprises monomeric acrylates and an N-substituted pyrolidone compound, to -treat the resulting synthetic resin surface with, for example, tannin acid, and then to provide a metal mirror by means of a metal-plating process.
:
-~2~9~65 PUN OWE -2- 17.2.1~4 The treatment of an acrylic plastic White -tannin acid known from the above mentioned United States Pa-te1Lt Specification has -the disadvantage that an adhererL-t silver mirror cannot be obtained. The treatment with -tannin acid known from the above-mentioned Netherlands Patent Apply-cation has the disadvantage that it can be applied only to a special synthetic resin, namely an acrylate synthetic resin which comprises an Substituted pyrolidone compound In the preparation of this special synthetic resin the pyrolidone compound is not completely copolymerized. The remaining pyrolidone molecules are volatile and in the course of time can adversely influence the quality of the provided metal mirror.
It is the object of the invention to provide a method which does not exhibit the above-mentioned dozed-vantages.
According to the invention this object is achieve achieved by means of a method of the type mentioned in the opening paragraph which is characterized in that the surface of a synthetic resin which comprises a carboxylic acid aside group is treated with tannin acid and is then provided with a metal mirror by means of an elec-troless metallization process, and that the surface of a synthetic resin which is a polyester, a polyolefine or a polyolefine containing halogen atom(s) or aromatic group(s) as subset-tents is subjected to an oxidizing -treatment, is -then treated with tannin acid, and is furthermore provided with a metal mirror by means of an electroless me-talliza-tion process.
The invention is based on the recognition trained by Applicants -that a pretreatment with tannin acid, in particular in combination with an oxidizing pretreatment step, has a more universal character and can be applied to the above-mentioned types of synthetic resin, in which after metallisa-tion, a very adherent metal mirror is ox-twined. Tile metal mirror also remains bonded to the sync Thetis resin sL1rLace after ageirlg tests, for employ a cyclic moisture test.
I
Ply 10.~L~9 -3- 1'7.2.198L~
In a favorably embodiment, a Sirius Or pull-imide, polyamide, polyurethane or pull re-tha1-e)acrylate which all comprise a carboxy~Lic acid aside group ( I ), is treated with -tannin acid, which -treatment may be pro-ceded by an oxidizing treatment and -then provided with a metal mirror by using an electroless metalliza-tion process.
I-n a further ~avourable embodiment a surface owe polyethylene, polyvinyl chloride, polystyrene polyethylene tereph-tha:Late~ polyacrylate or polymethyLmethacrylate is subjected to a corona discharge, is -treated with -tannin acid, and is provided with a metal mirror by means of an electroless metallization process.
corona discharge is a known process in which a high voltage is applied between the synthetic resin sun-face and an electrode. As a result of electric discharge, high-energy particles will be formed, for example atomic oxygen, electrons :iOI19 and the like which impact against -the synthetic resin surface, the composition oath sync Thetis resin at -the surface varying and in particle oxygen being bound -to -the surface of the synthetic resin.
The synthetic resin surface is oxidized and obtains a hydrophilic character.
In anther favorably embodiment of -the method in accordance with -the invention a Sirius of polyvinyl chloride or po:Lycar'bonate is -treated with chronic acid, -then with tannin acid, and is provided Wyeth a metal mirror 'by means of an e:Lec-troless rnetalliza-tion process.
The invention -will be described in greater detail with refererlce to the oiling example.
Example The surface of' a synthetic resin as recorded ill colui1ln -I of -the Table below is su'bJectecl ['Or a Lowe seconds to a coronae discharge by mccrls of a IF gerlerator having a sinusoidal alternating -voltage of TV and a t`reclllellcy ox 20-L~0 clue wt1icLl is conrlccl Clue Lo an electrical placed above the surface of the synthetic resin. The surface Ott tile syntilet-ic resin is then tLeate(:l Witty all aqueous Sue lion of tanrl:ic azalea rotor at most ore Malta a-t a tunneler-s PIN l0.~49 -4- 17-2-198~1 lure of I C. The concentration owe -tannin acid in the solution is no-t restricted -to narrow limits and may 'be chisel, by Jay owe example, between 0.1 and lo g ox -tannin assess per ire If desired the solution may also comprise water miscible organic solvents, or example, an organic acid, alcohol, acetone either or ester. The synthetic resin surface may be clipped in the solution ox tannin acrid. A solution ox tannin acid may also 'be sprayed or poured onto the surface to be treated.
The synthetic resins recorded in column 1 of the Table have been pretreated only with -tannin acid in a second series ox tests, no preceding oxidizing treatment being used.
after the -treatment -with -tannin acid, a metal mirror, for example an A mirror, is provided by electron less metal-plating. or -this purpose, the synthetic resin surface is treated with a sensitizing solution. In the case of providing an A layer, -the surface is treated for 1-60 seconds with a sensitizing solution which comprises an aqueous, acid Sneakily solution. The concentration of Sneakily is not restricted to narrow limits and is preferably from 0.01 to 1 g ox Sneakily per lithe, such as 0.1 g per lithe. The treatment may be carried out 'by means ox, or example, a dipping process, a pouring process or a spray-in process. The synthetic resin surface is then treated with -Thor actual me-tal-p~La-ting solutions, hence with the awakes metal salt solution, for example, an arnmoniacal silver nitrate solution no a-n aqueous reducing agent soul-Tony. on example owe` a suitable reducing agent is formal dchyde in combination with a sugar, or example sodium g'LIlconate. The meta:L-p:LatirIg solutions are preferably pro-v:idocl accorcI:ing to -the aerosol metaI-plat:irlg process in Welch tulle solutions are simultaneously slurred onto the syntIlet:ic -resin swirls. This process, as well as -tile metal salt solutions and education agent solutions used -the-reirl are described, OILY` example, in tile above-Irlet-ltioned literature roarers technical ProceediIIgs etc.". Various mutilating chemicals are commercially available frown PUN 10.S49 I l7.2.1984 for example, Messrs. Ermax, London Laboratories Lid or Merck.
The bonding of -the silver layer thus platted on the underlying synthetic resin surface is tested according to -the so-called diamond scratching -test (DIN 53151). Act cording to this standard test, twelve scratches are pro-voided in the surface of` the metal layer so as to extend over the whole width of -the metal layer. The pattern of sorts comprises 6 parallel sureties having a mutual lo distance of 1 mm which are crossed at right angles by likewise 6 parallel scratches having a mutual distance of 1 mm so that the pattern of scratches comprises 25 areas of 1 mm . An adhesive tape is pressed on the pattern of sureties and is then pulled off from -the surface. The extent of bonding is expressed in numbers 0-5, ill which :
0 = optimum bonding; 0 areas worn loose.
1 = good bonding; -l-5 areas oarlock loose
2 = reasonable bonding; Lowe areas work loose.
- 3 = insufficient bonding; l1-15 areas world loose.
4 = poor bonding; 16-20 areas world loose.
5 = no bonding; 21-25 areas work loose.
The results of the diamond scratch test are no-corded in columns 2 and 3 of -the Table.
-~2~9~5 PIN 1 O . 8 it 9 - 6 - -I '7 . . 1 9 8 4 TABLE
_ r e s t s lo o no it no t e s t Pretreatment: 'Pre-trentmen t ~;y7lthe tie resin Tony acid corona dozier . i .. ... a e i at polemical O O
polyurethane O , posy ( urea t'hn:rLe ) aureole t e O O
polka t:hy:LerL{e 5 O
lo us Lye vinyl e h 'L o n d e 5 O
pro lye Tory one 5 O
pro Lyethylene -terephthalate 5 O
polyirnide O O
polyaerylat e 5 O
lo polyme-thyl me-thacrylate 5 err e it &
polyvinyl chloride _ O
polyearbonate . O
It will be seen from -the Table that the pro--treatment with only tannin acid provides good results in synthetic resins having a carboxylic acid aside group, in this case polyamide, polyamide, polyurethane and posy 25 (L-l.rethane)aerylate. For the other synthetic resins recorded inn Thor Tabulate, a eorrlb:irled prc~tren-t;ment is rLecessiary ill wow aft ox:iclis:it~g t:rr?atmo~Lt~ Tory ~xarn-p:LQ a eoroniL ells-ch~l:tp;e our a t:renLrrle:l1l; Wyeth ehrolrl.ie ilCi(l, it .'illC(`C.`t,`dOCl ho it trOi~t;rllf~nl; Wit to tarLt-L:i.e i~e:icl. rule .sy:rltlLot,;.e r(-~s-irls owe' two 30 pulse tour typo :r~eo:rclecl in the Tillable ore pull thy:Lenc?
Morph l;:ha:l,iL lye, pro 'LILAC rye Lyle to?, po:l,~rlllo they'll, ma l;hne:ry:l,ilL to Clyde o:Lyol:rhon;lto. Tic po.lyoLe:L`il-L~ syrl,t;l-lot:i,e rousers rQeo:rclecl ion Lowe Rowley wll:i,etl Moe by slyest Lyle ~eit:ll hooligan ntorll.s or will nrolllrlt:i.e Rowley cry ,oo,l,yotlLy:lorlo~ pol,yv-irLy:L ehlo-35 Rowley isle po:l.ystyrorLe~. Oilier rQp:ro.sorLI;ilt:ivos out' Lyle said Lopez owl` .syt1l;hc~l,-i.e Rosen, ['or e~calTIpL(? po:Lyr)-ropy:l.e~r-o, nlny rl:L.~i<) I Ills (clue C I roll Lily I'll toll 3 tllo(l ill it CO to LOWE-, ~-~ wow ho 1;:1-1 o I, n v n l; I o n .
:1229~65 PUN 10.~49 -7- l7.2.19S4 Tile combined pretreatment of a corona discharge and tannin acid presents -the advantage that the metal mirror can be provided very accurately on certain parts of the synthetic resin surface. This is because a corona disk charge can be carried out very accurately in which there exists a sharp boundary between parts of the surface which have been subjected to a corona discharge and parts which have not been subjected to a corona discharge.
The method according to the invention may be used in the metallization of all kinds of products of synthetic resin, in particular optical components, for example mirrors. The method according to the invention is suitable in particular for providing a metal mirror on a synthetic resin surface which has a finely de-tailed struck lure which may not or only slightly be attacked during -the metalliza-tion. This applies in particular to the provision of a metal mirror on an optically readable information disc which has an optically readable information track of in-formation areas situated alternately at a higher level and at a lower level on one or both stales. The areas have very small dimensions in which -the difference in height is Ox loo 2 sum and the length of the areas is between Owe and 3 sum. The disc is known by -the trade names Laser vision and Compact Disc. The disc is usually manufactured from an acrylate synthetic resin, me-thacrylate synthetic resin or polycarbonate. On the side of the information track, the disc is coated with a metal layer, for example a silver layer. The silver layer must follow the contours of the information track very accurately and be firmly bonded -to the synthetic resin substrate. The difference in level between the information areas must be maintained during and after providing -the metal layer because -this difference is decisive of the quality of -the reproduction (reading) of -the stored information. moreover -the provision of the metal layer must not cause cloudiness of the synthetic resin of -the synthetic resin-metal interface. These wreck-foments are satisfied if the metal layer is provided act cording to the method of the invention.
:~2Z926~
PUN lQ.SI~9 -S- 17.2.19S4 In addition to the silver layer mentioned here-in before, other metal layers may also be provided on a synthetic resin surface by means of -the method according -to the invention while using an electroless metallization process. A copper layer, for example, can also be provided very readily by the electroless metallization process according to the present invention. After the required pro-treatment, as disclosed herein before, the synthetic resin surface to be copper-plated, is sensitized with an acid Sneakily solution. The sensitized surface is treated with an aqueous ammonia Cal silver salt solution in which a redo reaction takes place at the surface according -to the equation Snow+ + jag+ -I jag + Snow+. The resulting sun-face which comprises one or a few monolayer of A is then provided with a copper layer by using an ammonia Cal cuprous salt solution and an acid. This type of copper plating is known per so, as the disproportioning process and is desk cried inter aria in Technical Proceedings sty Annular Convention of the American Electroplates Society, p. ll~7, right-hand column and in German Of~enlegungsschrift 2,527, og6 .
The results of the diamond scratch test are no-corded in columns 2 and 3 of -the Table.
-~2~9~5 PIN 1 O . 8 it 9 - 6 - -I '7 . . 1 9 8 4 TABLE
_ r e s t s lo o no it no t e s t Pretreatment: 'Pre-trentmen t ~;y7lthe tie resin Tony acid corona dozier . i .. ... a e i at polemical O O
polyurethane O , posy ( urea t'hn:rLe ) aureole t e O O
polka t:hy:LerL{e 5 O
lo us Lye vinyl e h 'L o n d e 5 O
pro lye Tory one 5 O
pro Lyethylene -terephthalate 5 O
polyirnide O O
polyaerylat e 5 O
lo polyme-thyl me-thacrylate 5 err e it &
polyvinyl chloride _ O
polyearbonate . O
It will be seen from -the Table that the pro--treatment with only tannin acid provides good results in synthetic resins having a carboxylic acid aside group, in this case polyamide, polyamide, polyurethane and posy 25 (L-l.rethane)aerylate. For the other synthetic resins recorded inn Thor Tabulate, a eorrlb:irled prc~tren-t;ment is rLecessiary ill wow aft ox:iclis:it~g t:rr?atmo~Lt~ Tory ~xarn-p:LQ a eoroniL ells-ch~l:tp;e our a t:renLrrle:l1l; Wyeth ehrolrl.ie ilCi(l, it .'illC(`C.`t,`dOCl ho it trOi~t;rllf~nl; Wit to tarLt-L:i.e i~e:icl. rule .sy:rltlLot,;.e r(-~s-irls owe' two 30 pulse tour typo :r~eo:rclecl in the Tillable ore pull thy:Lenc?
Morph l;:ha:l,iL lye, pro 'LILAC rye Lyle to?, po:l,~rlllo they'll, ma l;hne:ry:l,ilL to Clyde o:Lyol:rhon;lto. Tic po.lyoLe:L`il-L~ syrl,t;l-lot:i,e rousers rQeo:rclecl ion Lowe Rowley wll:i,etl Moe by slyest Lyle ~eit:ll hooligan ntorll.s or will nrolllrlt:i.e Rowley cry ,oo,l,yotlLy:lorlo~ pol,yv-irLy:L ehlo-35 Rowley isle po:l.ystyrorLe~. Oilier rQp:ro.sorLI;ilt:ivos out' Lyle said Lopez owl` .syt1l;hc~l,-i.e Rosen, ['or e~calTIpL(? po:Lyr)-ropy:l.e~r-o, nlny rl:L.~i<) I Ills (clue C I roll Lily I'll toll 3 tllo(l ill it CO to LOWE-, ~-~ wow ho 1;:1-1 o I, n v n l; I o n .
:1229~65 PUN 10.~49 -7- l7.2.19S4 Tile combined pretreatment of a corona discharge and tannin acid presents -the advantage that the metal mirror can be provided very accurately on certain parts of the synthetic resin surface. This is because a corona disk charge can be carried out very accurately in which there exists a sharp boundary between parts of the surface which have been subjected to a corona discharge and parts which have not been subjected to a corona discharge.
The method according to the invention may be used in the metallization of all kinds of products of synthetic resin, in particular optical components, for example mirrors. The method according to the invention is suitable in particular for providing a metal mirror on a synthetic resin surface which has a finely de-tailed struck lure which may not or only slightly be attacked during -the metalliza-tion. This applies in particular to the provision of a metal mirror on an optically readable information disc which has an optically readable information track of in-formation areas situated alternately at a higher level and at a lower level on one or both stales. The areas have very small dimensions in which -the difference in height is Ox loo 2 sum and the length of the areas is between Owe and 3 sum. The disc is known by -the trade names Laser vision and Compact Disc. The disc is usually manufactured from an acrylate synthetic resin, me-thacrylate synthetic resin or polycarbonate. On the side of the information track, the disc is coated with a metal layer, for example a silver layer. The silver layer must follow the contours of the information track very accurately and be firmly bonded -to the synthetic resin substrate. The difference in level between the information areas must be maintained during and after providing -the metal layer because -this difference is decisive of the quality of -the reproduction (reading) of -the stored information. moreover -the provision of the metal layer must not cause cloudiness of the synthetic resin of -the synthetic resin-metal interface. These wreck-foments are satisfied if the metal layer is provided act cording to the method of the invention.
:~2Z926~
PUN lQ.SI~9 -S- 17.2.19S4 In addition to the silver layer mentioned here-in before, other metal layers may also be provided on a synthetic resin surface by means of -the method according -to the invention while using an electroless metallization process. A copper layer, for example, can also be provided very readily by the electroless metallization process according to the present invention. After the required pro-treatment, as disclosed herein before, the synthetic resin surface to be copper-plated, is sensitized with an acid Sneakily solution. The sensitized surface is treated with an aqueous ammonia Cal silver salt solution in which a redo reaction takes place at the surface according -to the equation Snow+ + jag+ -I jag + Snow+. The resulting sun-face which comprises one or a few monolayer of A is then provided with a copper layer by using an ammonia Cal cuprous salt solution and an acid. This type of copper plating is known per so, as the disproportioning process and is desk cried inter aria in Technical Proceedings sty Annular Convention of the American Electroplates Society, p. ll~7, right-hand column and in German Of~enlegungsschrift 2,527, og6 .
Claims (4)
1. A method of providing a metal mirror on an article of which at least the surface on which the metal mirror is to be provided is manufactured from a synthetic resin, char-acterized in that the surface of a synthetic resin which comprises a carbodylic acid amide group is treated with tannic acid and is then provided with a metal layer by means of an electroless metallization process, and that the surface of a synthetic resin which is a polyester, a poly-olefine or a polyolefine containing halogen atom(s) or aromatic group(s) as substituents, is subjected to an oxidising treatment, is then treated with tannic acid and is furthermore provided with a metal mirror by means of an electroless metallization process.
2. A method as claimed in Claim 1, characterized in that a synthetic resin surface which comprises polyimide, polyamide, polyurethane or poly(urethane)acrylate, is treated with tannic acid, which treatment may be preceded by an oxidising treatment and is then provided with a metal mirror by using an electroless metallization process.
3. A method as claimed in Claim 1, characterized in that a surface of polyethylene, polyvinyl chloride, poly-styrene, polyethylene terephthalate, polyacrylate or polymethyl methacrylate is subjected to a corona discharge, is treated with tannic acid, and is provided with a metal mirror by means of an electroless metallization process.
4. A method as claimed in Claim 1, characterized in that a surface of polyvinyl chloride or polycarbonate is treated with chromic acid, is then treated with tannic acid, and is provided with a metal mirror by means of an electro-less metallization process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8304084A NL8304084A (en) | 1983-11-29 | 1983-11-29 | METHOD FOR APPLYING A METAL MIRROR. |
| NL8304084 | 1983-11-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229265A true CA1229265A (en) | 1987-11-17 |
Family
ID=19842782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000468452A Expired CA1229265A (en) | 1983-11-29 | 1984-11-22 | Method of providing a metal mirror |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0149861B1 (en) |
| JP (1) | JPS60131974A (en) |
| AU (1) | AU584068B2 (en) |
| CA (1) | CA1229265A (en) |
| DE (1) | DE3478863D1 (en) |
| NL (1) | NL8304084A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU641231B2 (en) * | 1990-03-22 | 1993-09-16 | Monsanto Company | Electrolessly deposited metal holograms |
| JP5117656B2 (en) * | 2001-09-28 | 2013-01-16 | セーレン株式会社 | Electroless plating pretreatment method and conductive material using the same |
| FR2934609B1 (en) | 2008-07-30 | 2011-07-22 | Jet Metal Technologies | NON-ELETROLYTIC METHOD FOR ONLINE METALLIZATION OF PROJECTION SUBSTRATES WITH PRECONDITIONAL SURFACE TREATMENT AND DEVICE FOR IMPLEMENTING THE METHOD |
| JP5206630B2 (en) | 2009-08-27 | 2013-06-12 | 日立電線株式会社 | Electrical connection component and electrical connection method using flexible harness |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3094430A (en) * | 1961-12-11 | 1963-06-18 | John E Marshall Jr | Method of applying mirror coating to acrylic base |
| CH610596A5 (en) * | 1977-02-16 | 1979-04-30 | Ebauches Sa | |
| NL8103375A (en) * | 1981-07-16 | 1983-02-16 | Philips Nv | METHOD FOR THE MANUFACTURE OF A PLASTIC ARTICLE WITH A METAL LAYER. |
-
1983
- 1983-11-29 NL NL8304084A patent/NL8304084A/en not_active Application Discontinuation
-
1984
- 1984-11-20 DE DE8484201682T patent/DE3478863D1/en not_active Expired
- 1984-11-20 EP EP84201682A patent/EP0149861B1/en not_active Expired
- 1984-11-22 CA CA000468452A patent/CA1229265A/en not_active Expired
- 1984-11-27 AU AU35901/84A patent/AU584068B2/en not_active Ceased
- 1984-11-27 JP JP24883384A patent/JPS60131974A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU3590184A (en) | 1985-06-06 |
| NL8304084A (en) | 1985-06-17 |
| DE3478863D1 (en) | 1989-08-10 |
| JPS60131974A (en) | 1985-07-13 |
| EP0149861B1 (en) | 1989-07-05 |
| EP0149861A2 (en) | 1985-07-31 |
| EP0149861A3 (en) | 1985-09-11 |
| AU584068B2 (en) | 1989-05-18 |
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