US3666527A - Method of electroless deposition of metals with improved sensitizer - Google Patents

Method of electroless deposition of metals with improved sensitizer Download PDF

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US3666527A
US3666527A US60091A US3666527DA US3666527A US 3666527 A US3666527 A US 3666527A US 60091 A US60091 A US 60091A US 3666527D A US3666527D A US 3666527DA US 3666527 A US3666527 A US 3666527A
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solution
plating
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sensitizing
metal
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Nathan Feldstein
Thomas Stephen
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RCA Corp
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    • 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
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition

Definitions

  • Certain metals can be plated on non-metallic surfaces by an autocatalytic electroless process in which the surface is first treated with a sensitizing solution, then with an activating solution which precipitates nucleating centers.
  • ceramics and many synthetic resins can be provided with coatings of nickel or copper, for example, which may or may not be later covered with a heavier layer of metal by electroplating.
  • the sensitizing solution most commonly used in the past contains Sn+ ions generally formed from the salt stannous chloride. This material has proved to be quite satisfactory for electroless plating of metals on most nonmet-allic materials. However, there are certain plastics, such as Teflon, Lucite and silicone rubbers, as well as certain commercial photoresists, which cannot be satisfactorily plated by this method. The reason for the difficulty appears to be that these materials are unusually smooth and non-porous and are not readily wetted by aqueous solutions of stannous salts.
  • One object of the present invention is to provide an improved method of autocatalytically electrolessly depositing metals on certain non-metallic substrates which are difiicult to wet.
  • Another object of the invention is to provide an improved sensitizing solution for autocatalytically electrolessly depositing metals on non-metallic substrates.
  • the plate is permitted to remain in the plating bath until either a good uniform plating is obtained or it is apparent that no further deposit is being obtained on unplated areas. This is usually a few minutes.
  • the following table shows the effect of adding varying amounts of SnCL, solution to a conventional SnCl sensitizing solution.
  • the SnCl, stock solution was prepared by dissolving crystalline material in water and permitting the solution to stand for about one week at room temperature before using. It has been found that an aging effect, not fully understood, occurs in this solution. Less of the aged solution is required to impart the improved wetting to the sensitizer. The aging efiect may be due to an hydrolysis reaction taking place.
  • Example II With all conditions and treating and plating solutions remaining the same as in Example I except the proportion of stannic ion, Mylar tape coated with AZ-l350, a positive acting photoresist, was plated with nickel from the same nickel-boron bath. In this case, when the concentration of stannic ion was above zero and up to '7.5X10- moles/liter, only patchy plating was obtained. Above about 1.25 X moles/liter good plating was obtained although this increase in coverage was again gradual. With no stannic ion added, only little plating was obtained.
  • Example III In another test run using a nickel-boron plating bath, as described in Example I, on AZ-1350 photoresist, the sensitizing solution was made up by adding varying amounts of powdered SnCl -5-H O (reagent grade) to freshly prepared SnCl solution.
  • the stock solution from which the stannous ion solution was prepared comprised 214 gms. SnCl -2H O (Baker reagent grade) and 290 cc. conc. HCl.
  • the actual solution used for the run contained 64x10 molar concentration of Sn+ ion and an HCl content of 0.19 M.
  • Example IV iWith conditions otherwise the same as in Example HI, the molar concentrations of Sn+ ion used was increased to 12.8Xl0- molar and the HCl to 0.38 Patchy plating on AZ-1350 photoresist from the same nickelboron plating bath was obtained using molar concentration of Sn+ ion below about 10.4)(10' molar. Good, uniform plating was obtained above about 104x10 molar.
  • the copper plating bath had the following composition.
  • E.D.T.A. Ethylene diaminetetra-acetic acid (40% solution of the sodium salt) -gm-s 36.5
  • the sensitizing solution contained Sn+ ion 6.4X10- molar and had an HCl content of 0.19 molar. To this was added varying amounts of stannic chloride solution that had been aged for a minimum of one week.
  • Example VI Using the same copper-depositing bath as in Example V and Sn+ ion concentration of 6.4X10- moles, an experimental run was made to see if the quality of the plating was affected by using increasingly high ratios of Sn ion to Sn+ ion, with the following results.
  • the substrate used was Teflon.
  • stannic ion may be generated.
  • agents capable of oxidizing the Sn ion to Sn ion such as iodine or permangauates, for example.
  • Another method is by exposing the Sn+ solution to U.V. light for a period of time. By merely heating the Sn+ solution in air, some of the Sn ion is converted to Su
  • the addition of Sn ion is preferred because the amount can be more accurately controlled and can conveniently be used in production facilities.
  • the pH of the solutions was generally below one and the solutions were clear. At pH values around 1.5 the solutions become turbid. It is therefore preferred that the pH value he kept below about 1.5 and, more preferably, below one.
  • a molar ratio of divalent tin ion to tetravalent tin ion between about 1:1 and 1000:1 has been found to be operative.
  • stanic chloride is given as an example of a suitable tin compound to use to add So ion in the present invention, it will be understood that other soluble stannic compounds can be used.
  • the improved method of the present invention is also of particular interest in the making of printed circuit boards; especially boards having small-diameter through holes which must be plated with metal.
  • Materials commonly used for printed circuit substrates are phenolic resinimpregnated fibrous materials, epoxy resin-impregnated boards and glass fiber-epoxy resin boards.
  • the boards are usually laminates of several thin sheets.
  • the improved sensitizers described herein wet these materials very well. The sensitizers wet so efliciently that very small diameter through holes, usually very diflicult to plate electrolessly with previously used Sn+ sensitizers, can now be plated very well.
  • the improvement is due not only to the increased wetting ability of the present sensitizers but also due to the fact that they are not degraded by air agitation. Agitation of the bath is necessary to cause solutions to flow through the holes. Air agitation adversely affects Sn+ sensitizers.
  • a method for electrolessly plating a surface with a metal comprising the steps of sensitizing the surface with a sensitizing solution made by mixing separate sources of divalent tin ion and tetravalent tin ion in a molar ratio from about 1:1 to about 1000: 1, the solution having a pH lower than about 1.5, the tetravalent tin ion being prepared as a separate solution of a stannic salt which is aged for a time before combining it with the source of divalent tin ion, treating the sensitized surface with a catalyzing solution so as to provide catalytic nucleating centers thereon, and plating said metal on the catalyzing surface by contacting the surface with an electroless metal plating bath.
  • said surface is a smooth, dense, difficultly wettable plastic.

Abstract

METHOD FOR AUTOCATALYTICALLY ELECTROLESSLY PLATING A DIELECTRIC SURFACE WITH A METAL SUCH AS NICKEL, COBALT OR COPPER COMPRISING SENSITIZING THE SURFACE WITH AN IMPORVED SENSITIZING SOLUTION COMPRISING BOTH DIVALENT TIN ION AND TETRAVALENT TIN ION, THE SOLUTION HAVING A PH LESS THAN ABOUT 1.5, TREATING THE SENSITIZED SURFACE WITH A CATALYZING SOLUTION TO PROVIDE CATALYTIC NUCLEATING CENTERS, AND PLATING THE METAL ON THE CATALYZED SURFACE. THE IMPROVED SENSITIZING SOLUTION PERMITS PLATING ON SMOOTH, DENSE, WATER REPELLENT PLASTIC SURFACES SUCH AS TEFLON, LUCITE, SILICONE RUBBERS AND MYLAR.

Description

United States Patent METHOD OF ELECTROLESS DEPOSITION OF METALS WITH IMPROVED SENSITIZER Nathan Feldstein, Kendall Park, and Thomas Stephen Lancsek, Mercer, N.J., assignors to RCA Corporation No Drawing. Filed July 31, 1970, Ser. No. 60,091
Int. Cl. B44d 1/092; C23c 17/02 US. Cl. 117-47 A 8 Claims ABSTRACT OF THE DISCLOSURE Method for autocatalytically electrolessly plating a dielectric surface with a metal such as nickel, cobalt or copper comprising sensitizing the surface with an improved sensitizing solution comprising both divalent tin ion and tetravalent tin ion, the solution having a pH less than about 1.5, treating the sensitized surface with a catalyzing solution to provide catalytic nucleating centers, and plating the metal on the catalyzed surface. The improved sensitizing solution permits plating on smooth, dense, water repellent plastic surfaces such as Teflon, Lucite, silicone rubbers and Mylar.
BACKGROUND OF THE INVENTION Certain metals can be plated on non-metallic surfaces by an autocatalytic electroless process in which the surface is first treated with a sensitizing solution, then with an activating solution which precipitates nucleating centers. In this way ceramics and many synthetic resins can be provided with coatings of nickel or copper, for example, which may or may not be later covered with a heavier layer of metal by electroplating.
The sensitizing solution most commonly used in the past contains Sn+ ions generally formed from the salt stannous chloride. This material has proved to be quite satisfactory for electroless plating of metals on most nonmet-allic materials. However, there are certain plastics, such as Teflon, Lucite and silicone rubbers, as well as certain commercial photoresists, which cannot be satisfactorily plated by this method. The reason for the difficulty appears to be that these materials are unusually smooth and non-porous and are not readily wetted by aqueous solutions of stannous salts. As a result, when one attempts to deposit metal autocatalytically on one of these materials with no surface toughening, using conventional stannous salt sensitizers and conventional activators, such as palladium chloride, plating is spotty and otherwise non-uniform.
It should be noted that, in general, those who have used acidic solutions of stannous salts as electroless plating sensitizers, have tried to keep the tin ion in the divalent state by methods such as keeping metallic tin or other reducing agents such as sugars in the shelf stock solutions.
OBJECTS OF THE JNVENTION One object of the present invention is to provide an improved method of autocatalytically electrolessly depositing metals on certain non-metallic substrates which are difiicult to wet.
Another object of the invention is to provide an improved sensitizing solution for autocatalytically electrolessly depositing metals on non-metallic substrates.
DESCRIPTION OF PREFERRED EMBODIMENTS It has now been found, unexpectedly, that if stannic ion is added to conventional acid sensitizing solutions containing stannous ion, and the resulting solution is used to treat difiicult-to-plate non-metallic surfaces, in the usual way, these sensitized surfaces (after the usual activation 3,666,527 Patented May 30, 1972 "ice Example I Substrate: smooth Teflon plate with no mechanical or chemical roughening.
Procedure: after the Teflon plate was chemically cleaned with a detergent solution it was immersed in a sensitizing solution comprising SnCl having the concentration of 6.4)(10 moles/liter, an HCl content of 0.19 mole, and varying amounts of SnCl The treated plate was removed from the sensitizing bath, rinsed and immersed in an activating bath of PdCl containing 1 g. of PdC12 and 1 cc. conc. HCl per liter (remainder water). .After a few seconds in the activating bath, the plate was again removed and rinsed, after which it was immersed in a nickel-depositing bath at 25 C. having the following composition:
In one liter of solution:
Dimethylamine borane1.5 g. NiSO .6H O-25 g. Na 'P O .10I-I O-50 g. NH OH (58% conc.)25 cc. Water-remainder.
The plate is permitted to remain in the plating bath until either a good uniform plating is obtained or it is apparent that no further deposit is being obtained on unplated areas. This is usually a few minutes.
The following table shows the effect of adding varying amounts of SnCL, solution to a conventional SnCl sensitizing solution. In this case, the SnCl, stock solution was prepared by dissolving crystalline material in water and permitting the solution to stand for about one week at room temperature before using. It has been found that an aging effect, not fully understood, occurs in this solution. Less of the aged solution is required to impart the improved wetting to the sensitizer. The aging efiect may be due to an hydrolysis reaction taking place.
Cone. of SnCL, (moles/liter): 1 I Plating results 0 Practically no wetting or plating. 2.5 X 10* Spotty plating. 5.0x l0- Do. 7.5 x 10 Do. 1.25 X 10* Do. 2.0)(10' Good plating. 2.5 X 10- Do. 325x16 Do. 3.75 10 Do.
In the sensitizing bath which also contained 6.4)(10- moles/liter of SnClz.
NOTE.AS the amount of SnCli was increased, coverage of plating became better ni gradual increments. There was actually no abrupt change from spotty to good."
Example II With all conditions and treating and plating solutions remaining the same as in Example I except the proportion of stannic ion, Mylar tape coated with AZ-l350, a positive acting photoresist, was plated with nickel from the same nickel-boron bath. In this case, when the concentration of stannic ion was above zero and up to '7.5X10- moles/liter, only patchy plating was obtained. Above about 1.25 X moles/liter good plating was obtained although this increase in coverage was again gradual. With no stannic ion added, only little plating was obtained.
Example III In another test run using a nickel-boron plating bath, as described in Example I, on AZ-1350 photoresist, the sensitizing solution was made up by adding varying amounts of powdered SnCl -5-H O (reagent grade) to freshly prepared SnCl solution. The stock solution from which the stannous ion solution was prepared comprised 214 gms. SnCl -2H O (Baker reagent grade) and 290 cc. conc. HCl. The actual solution used for the run contained 64x10 molar concentration of Sn+ ion and an HCl content of 0.19 M.
Patchy plating was obtained with molar concentrations of Sn ion below about 0.86X 10- Above about 0. 86Xl0- molar, satisfactory, uniform plating resulted.
Activation procedure was the same as in Example 1.
Example IV iWith conditions otherwise the same as in Example HI, the molar concentrations of Sn+ ion used was increased to 12.8Xl0- molar and the HCl to 0.38 Patchy plating on AZ-1350 photoresist from the same nickelboron plating bath was obtained using molar concentration of Sn+ ion below about 10.4)(10' molar. Good, uniform plating was obtained above about 104x10 molar.
Example V Copper was deposited on a smooth Teflon substrate using the following procedure. After cleaning the substrate, it was immersed in a sensitizer solution containing Sn and Sn+ ions as set forth below, treated with a PdCl activating solution as in the previous examples, and then immersed in a copper plating bath. The copper plating bath had the following composition.
Per liter CuSO '5H- O -.gms-.. 7.5 Ethylene diaminetetra-acetic acid (E.D.T.A.) (40% solution of the sodium salt) -gm-s 36.5
NaOI-I g s 20.0
NaCN gm 0.1
HCHO (37% solution) ml 40 Water to make 1000 ml.
The sensitizing solution contained Sn+ ion 6.4X10- molar and had an HCl content of 0.19 molar. To this was added varying amounts of stannic chloride solution that had been aged for a minimum of one week.
(Gradual increase in plating coverage with increasing amounts of Sn+ ion.)
Example VI Using the same copper-depositing bath as in Example V and Sn+ ion concentration of 6.4X10- moles, an experimental run was made to see if the quality of the plating was affected by using increasingly high ratios of Sn ion to Sn+ ion, with the following results. The substrate used was Teflon.
.4 Cone. of Sn+ ion (molar) 2 Plating results 8.0 X 10- Good. 1 X 10- Do. 2 X 10 Do. 3 X 10- Do. 4x10 Do. 5 X 10- D0. 6 X 10- iBorderline. 7 X 10-- Patchy. 8 X 10- Do.
It was therefore concluded that, in each case, there is likely to be an upper limit to the amount of Sn+ ion in relation to Sn+ ion but this will differ with different plating solutions, different substrates and other conditions.
Although a preferred way to add the Sn* ion is by a solution which has been aged, since less tin (-l-IV) is required using this procedure, there are other ways in which stannic ion may be generated. One of these is by adding agents capable of oxidizing the Sn ion to Sn ion, such as iodine or permangauates, for example. Another method is by exposing the Sn+ solution to U.V. light for a period of time. By merely heating the Sn+ solution in air, some of the Sn ion is converted to Su In practice, the addition of Sn ion is preferred because the amount can be more accurately controlled and can conveniently be used in production facilities.
For further information on other previously-known stannous chloride sensitizing solutions to which stannic ion can be added as described herein, see, for example, Metallic Coating of Plastics by William Goldie, Electrochemical Publications Limited, London (1968) Chapter 5.
In the examples given above, the pH of the solutions was generally below one and the solutions were clear. At pH values around 1.5 the solutions become turbid. It is therefore preferred that the pH value he kept below about 1.5 and, more preferably, below one.
In the present method it is believed that the improved results are due to the presence of a complex of Sn+ and Sn.
In general, a molar ratio of divalent tin ion to tetravalent tin ion between about 1:1 and 1000:1 has been found to be operative.
Although stanic chloride is given as an example of a suitable tin compound to use to add So ion in the present invention, it will be understood that other soluble stannic compounds can be used.
The improved method of the present invention is also of particular interest in the making of printed circuit boards; especially boards having small-diameter through holes which must be plated with metal. Materials commonly used for printed circuit substrates are phenolic resinimpregnated fibrous materials, epoxy resin-impregnated boards and glass fiber-epoxy resin boards. The boards are usually laminates of several thin sheets. The improved sensitizers described herein wet these materials very well. The sensitizers wet so efliciently that very small diameter through holes, usually very diflicult to plate electrolessly with previously used Sn+ sensitizers, can now be plated very well. The improvement is due not only to the increased wetting ability of the present sensitizers but also due to the fact that they are not degraded by air agitation. Agitation of the bath is necessary to cause solutions to flow through the holes. Air agitation adversely affects Sn+ sensitizers.
What is claimed is:
1. A method for electrolessly plating a surface with a metal comprising the steps of sensitizing the surface with a sensitizing solution made by mixing separate sources of divalent tin ion and tetravalent tin ion in a molar ratio from about 1:1 to about 1000: 1, the solution having a pH lower than about 1.5, the tetravalent tin ion being prepared as a separate solution of a stannic salt which is aged for a time before combining it with the source of divalent tin ion, treating the sensitized surface with a catalyzing solution so as to provide catalytic nucleating centers thereon, and plating said metal on the catalyzing surface by contacting the surface with an electroless metal plating bath. 2. A method according to claim 1 in which said surface is a smooth, dense, difficultly wettable plastic.
3. A method according to claim 2 in which said surface is Teflon.
4. A method according to claim 1 in which said metal is nickel.
5. A method according to claim 1 in which said metal is copper.
6. A method according to claim 1 in which said surface is a phenolic resin impregnated fibrous material.
7. A method according to claim 1 in which said surface is an epoxy resin-impregnated material.
8. A method according to claim 1 in which said surface is a glass fiber-epoxy board.
References Cited UNITED STATES PATENTS 2,282,511 5/1942 Bradley 117130 3,033,703 5/1962 Schneble et al 117-47 3,134,690 5/ 1964 Eriksson 117-47 X 3,167,491 1/1965 Harrison et al. 117138.8 X 3,245,826 4/1966 Luce et a1 117-47 3,573,973 4/1971 Drotar et al. 117-47 A 3,616,296 10/1971 Bernhardt et al. 117-47 A T. G. DAVIS, Assistant Examiner US. Cl. X.R.
117138.8 R, 138.8 UA, 138.8 UP, 160 R, 213
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3877965A (en) * 1970-09-28 1975-04-15 Rohm & Haas Conductive nylon substrates and method of producing them
US3982054A (en) * 1972-02-14 1976-09-21 Rca Corporation Method for electrolessly depositing metals using improved sensitizer composition
US3993801A (en) * 1975-02-18 1976-11-23 Surface Technology, Inc. Catalytic developer
US4082899A (en) * 1976-09-07 1978-04-04 Nathan Feldstein Method of applying catalysts for electroless deposition and article
DE2856375A1 (en) * 1977-12-28 1979-08-02 Cbs Sony Records Inc METHOD OF MANUFACTURING RECORD MATRIX
US4301190A (en) * 1978-08-17 1981-11-17 Nathan Feldstein Pretreatment with complexing agent in process for electroless plating
US4396643A (en) * 1981-06-29 1983-08-02 Minnesota Mining And Manufacturing Company Radiation absorbing surfaces
US4398462A (en) * 1979-05-30 1983-08-16 Tdk Electronics Co., Ltd. Hot melt screen printing machine
US4582111A (en) * 1981-06-29 1986-04-15 Minnesota Mining And Manufacturing Company Radiation absorbing surfaces
US4582885A (en) * 1978-07-20 1986-04-15 Minnesota Mining And Manufacturing Company Shaped plastic articles having replicated microstructure surfaces
US4853320A (en) * 1987-09-16 1989-08-01 U.S. Philips Corporation Method of locally providing metal on a surface of a substrate
US5403650A (en) * 1982-04-27 1995-04-04 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate and products produced thereby
US20110105366A1 (en) * 2007-06-18 2011-05-05 Illumina, Inc. Microfabrication methods for the optimal patterning of substrates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3245826A (en) * 1963-06-12 1966-04-12 Clevite Corp Magnetic recording medium and method of manufacture
US3573973A (en) * 1967-11-13 1971-04-06 Ibm High speed additive circuit process
DE1905097A1 (en) * 1969-02-01 1970-08-06 Dynamit Nobel Ag Process for the metallization of plastics

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3877965A (en) * 1970-09-28 1975-04-15 Rohm & Haas Conductive nylon substrates and method of producing them
US3982054A (en) * 1972-02-14 1976-09-21 Rca Corporation Method for electrolessly depositing metals using improved sensitizer composition
US3993801A (en) * 1975-02-18 1976-11-23 Surface Technology, Inc. Catalytic developer
US4082899A (en) * 1976-09-07 1978-04-04 Nathan Feldstein Method of applying catalysts for electroless deposition and article
DE2856375A1 (en) * 1977-12-28 1979-08-02 Cbs Sony Records Inc METHOD OF MANUFACTURING RECORD MATRIX
US4582885A (en) * 1978-07-20 1986-04-15 Minnesota Mining And Manufacturing Company Shaped plastic articles having replicated microstructure surfaces
US4301190A (en) * 1978-08-17 1981-11-17 Nathan Feldstein Pretreatment with complexing agent in process for electroless plating
US4398462A (en) * 1979-05-30 1983-08-16 Tdk Electronics Co., Ltd. Hot melt screen printing machine
US4396643A (en) * 1981-06-29 1983-08-02 Minnesota Mining And Manufacturing Company Radiation absorbing surfaces
US4582111A (en) * 1981-06-29 1986-04-15 Minnesota Mining And Manufacturing Company Radiation absorbing surfaces
US5403650A (en) * 1982-04-27 1995-04-04 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate and products produced thereby
US5565235A (en) * 1982-04-27 1996-10-15 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate
US4853320A (en) * 1987-09-16 1989-08-01 U.S. Philips Corporation Method of locally providing metal on a surface of a substrate
US20110105366A1 (en) * 2007-06-18 2011-05-05 Illumina, Inc. Microfabrication methods for the optimal patterning of substrates
US9677194B2 (en) 2007-06-18 2017-06-13 Illumina, Inc. Microfabrication methods for the optimal patterning of substrates

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CA945838A (en) 1974-04-23
GB1348793A (en) 1974-03-20
JPS5223982B1 (en) 1977-06-28
FR2104816B1 (en) 1975-08-29
FR2104816A1 (en) 1972-04-21
AU3126671A (en) 1973-01-18

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