US2828194A - Etching - Google Patents

Etching Download PDF

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Publication number
US2828194A
US2828194A US612886A US61288656A US2828194A US 2828194 A US2828194 A US 2828194A US 612886 A US612886 A US 612886A US 61288656 A US61288656 A US 61288656A US 2828194 A US2828194 A US 2828194A
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US
United States
Prior art keywords
percent
etching
bath
acid
sulfated
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 - Lifetime
Application number
US612886A
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English (en)
Inventor
Charles W Hopkins
John A Easley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to DENDAT1071717D priority Critical patent/DE1071717B/de
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US612886A priority patent/US2828194A/en
Priority to FR1189955D priority patent/FR1189955A/fr
Application granted granted Critical
Publication of US2828194A publication Critical patent/US2828194A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/42—Aqueous compositions containing a dispersed water-immiscible liquid

Definitions

  • ing surface such as a photoengraving
  • a plate of an acidsoluble metal such as magnesium, zinc, or one of their alloys is firstly coated with a light-sensitive coating or enamel, applied to the generally flat or cylindrical metal surface.
  • This coated surface is then exposed to light through a negative having an image thereon so as to produce a corresponding image on the coating.
  • the exposed coated surface is then "developed, forming an acid-resistant coating in the form of the image produced by the exposure.
  • This acid-resistant coating is further hardened by heating and the image-bearing surface of the plate is then subjected to etching by an acid.
  • This invention is directed to an etching technique which may be accomplished by providing an etching bath containing aqueous nitric acid, an immiscible organic liquid substantially unreactive with the aqueous nitric acid solution, and a water-soluble, anionic, surface-active half ester of sulfuric acid, containing at least one hydrophobic group therein, said hydrophobic group containing between 10 and 26 carbon atoms in an uninterrupted chain, said ester also containing at least 8 percent sulfation, the ester usually being derived from the sulfuric acid treatment of naturally-occurring fats, oils and waxes.
  • Suitable metals which may be etched by the process and bath of the present invention are magnesium, magnesium base alloys containing at least 85 percent magnesium, and zinc and zinc base alloys containing at least '90 percent zinc.
  • the surface of the metal is first coated uniformly with a lightsensitive material, exposed to light through a negative, developed, and, if necessary, heated to increase the acid resistance of the resist.
  • a lightsensitive material exposed to light through a negative, developed, and, if necessary, heated to increase the acid resistance of the resist.
  • Aqueous nitric acid for the bath of the present invention is employed in an amount by weight of the total bath between about .lfleasLgimstsenh i fil-ls. concentrations in the range of from 3 to 20 percent HNO being most generally useful, while a concentration of from 4 to 12.5 percent is preferred.
  • Suitable organic materials which may be used in the method and bath of the 5125- cut invention include, for example, the various petroleum fractions boiling in the range of to 390-C., such" as gasoline, benzine, kerosene, coal oil, and lubricating oils.
  • Other organic liquids which may be employed include tuipentine, perchloroethylene, the diethylpegggnes,
  • the a ngggnt gin; ganic liquid employed will vary with the type of metal sur ace to be processed, but will fall within the range of 1 t o p ercentby weight of the total bath and preferably is from 5 'to 8 percent.
  • a third corn onent of the bath e. g., a sulfated fat oil or W a sulfate-radical-containing, organic surface-active agent.
  • This component can further be described as containing at least in part a half ester of sulfuric acid, the component being water-soluble, anionic, and containing at least 8 percent sulfation, preferably at least 14 percent. Percentage of sulfation, as used herein, is intended to mean the average amount of sulfate (80,) contained in the molecule divided by the practical amount of sulfation possible multiplied by one hundred.
  • the hydrophobic portion of the surface-active agent must contain at least one aliphatic organic group containing at least 10 carbon atoms and not more than 26 carbon atoms, and preferably from 14 to 26 carbon atoms.
  • Suitable sulfated materials which may be used in the bath of the present invention include, for example, sulphated tall oil, sulfated castor oil, sulfated sperm oil, sulfated tallow, sulfated propyloleate, alkylarylpolyether sulfates, sulfated amides, sulfated alcohols, the monoglyceride ester of coconut oil sulfate, etc. These materials are generally available commercially under various trade names.
  • the amount of the third component employed is critical, the effective range of concentration being between 0.4 and 2.0 percent by weight of a total etching bath.
  • Monosulph Nopco Chemical Company-a sulfated castor oil having 45 percent sulfation containing 30 percent water, 2 percent sodium sulfate, 24 percent sulfated ester, 28 percent unreacted neutral oil and 16 percent sulfated acids and soap and free fatty acids
  • optimum effective concentration 1.16 percent.
  • the etching bath of the present invention forms a partially acid-resistant film on the resist-free metal surfaces, and when the bath is impinged against the surface to be etched in a direction normal to that surface, the film is broken.
  • the bath hits the sides of the relief the film is generally not broken because of insufficient striking force and etching of the sides (or undercutting) is substantially reduced.
  • an etching machine of the type disclosed in Patent No. 2,669,048, issued February 16, 1954, and entitled Etching Machine. In this machine elongated paddles dipping into the bath composition intermittently throw, by splashing, the etching bath composition in sheets upwardly against the image bearing side of the object being etched, e. g. a plate.
  • etch factor is defined as the ratio of the depth of the etch adjacent to a line of resist divided by one-half of the loss in width of metal immediately beneath the resist.
  • each of the baths was relatively stable and each bath gave a very favorable etch when conditions were adiusted.
  • 2,669,048, was provided and approxil masked and unmasked portions thereof an aqueous solumately 3 liters of water at a temperature of about 601 ti hi h c ntain (1) from 1 t 25 percent of HNO,, F. placed therein.
  • nitric acid of 42 liaume (2) a water-immiscible organic liquid substantially untechnical was added to make a final concentration O reactive with the aqueous nitric acid, and (3) between 0.4 a in the bath of Percent Next, Shfhclent MOHO- and 2.0 percent of a component which includes a watersulph P Chemia1C0mPanY-a 45 p n sulfifted soluble, anionic, sulfate-radical-containing, surface-active castor oil) to make a 1.22 percent final solution mixed agent containing at l t one h d hobi group of with sufficient diethyl-benzene to get a final concentration f m 10 to 26 ca b n atoms in an uninterrupted chain of 7 percent was added to the bath, and the volume and said agent containing at least 8 percent sulfation.
  • EXAMPLE 2 4o 4. The method of claim 2 wherein the organic oil is diethylbenzene.
  • the Turkey red oil contained approximately 22 percent sulfation, while the others contained between 10 and 20 percent sulfation, depending on the amount of reaction products remaining with the desired material after purification by the supplier.
  • An etching bath comprising a mixture of 1 to 25 percent nitric acid, a water-immiscible organic liquid sub- References Cited in the file of this patent UNITED STATES PATENTS Easley et a1. June 2, 1953 OTHER REFERENCES Schwartz-Perry: Surface Active Agents, publ. 1949, Interscience Pub. Inc., N. Y., p. 462, lines 7-11.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
US612886A 1956-09-28 1956-09-28 Etching Expired - Lifetime US2828194A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DENDAT1071717D DE1071717B (enrdf_load_stackoverflow) 1956-09-28
US612886A US2828194A (en) 1956-09-28 1956-09-28 Etching
FR1189955D FR1189955A (fr) 1956-09-28 1957-09-27 Gravure à l'acide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US612886A US2828194A (en) 1956-09-28 1956-09-28 Etching

Publications (1)

Publication Number Publication Date
US2828194A true US2828194A (en) 1958-03-25

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Family Applications (1)

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US612886A Expired - Lifetime US2828194A (en) 1956-09-28 1956-09-28 Etching

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US (1) US2828194A (enrdf_load_stackoverflow)
DE (1) DE1071717B (enrdf_load_stackoverflow)
FR (1) FR1189955A (enrdf_load_stackoverflow)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2981609A (en) * 1956-11-20 1961-04-25 United Aircraft Corp Etching bath for titanium and its alloys and process of etching
US3023138A (en) * 1959-06-12 1962-02-27 Dow Chemical Co Powderless etching bath and method of etching plates therewith
US3043693A (en) * 1957-02-06 1962-07-10 Trenton Times Corp Method and apparatus for making printing plates
US3108031A (en) * 1960-04-15 1963-10-22 Ernest N Hasala Apparatus for etching curved metal plates
US3296142A (en) * 1964-04-06 1967-01-03 Ball Brothers Co Inc Etching composition and method of etching
US3330765A (en) * 1965-10-01 1967-07-11 Dow Chemical Co Powderless etching bath and method of etching
US3340188A (en) * 1962-08-23 1967-09-05 Phillips Petroleum Co Drilling fluid
US3356550A (en) * 1964-03-16 1967-12-05 Boeing Co Chemical milling of aluminum alloys
US3376228A (en) * 1965-05-19 1968-04-02 Ball Brothers Co Inc Etching composition and method
US3394060A (en) * 1965-02-19 1968-07-23 Ellwood S. Douglas Process for electrolytically regenerating ferric chloride etching solutions
US3412032A (en) * 1965-02-01 1968-11-19 Revere Copper & Brass Inc Etching bath composition
US3417022A (en) * 1961-03-24 1968-12-17 Ball Brothers Co Inc Etching composition and method
US3793053A (en) * 1966-05-10 1974-02-19 Owens Illinois Inc Glass decoration

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2640765A (en) * 1951-02-12 1953-06-02 Dow Chemical Co Etching

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2640765A (en) * 1951-02-12 1953-06-02 Dow Chemical Co Etching

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2981609A (en) * 1956-11-20 1961-04-25 United Aircraft Corp Etching bath for titanium and its alloys and process of etching
US3043693A (en) * 1957-02-06 1962-07-10 Trenton Times Corp Method and apparatus for making printing plates
US3023138A (en) * 1959-06-12 1962-02-27 Dow Chemical Co Powderless etching bath and method of etching plates therewith
US3108031A (en) * 1960-04-15 1963-10-22 Ernest N Hasala Apparatus for etching curved metal plates
US3417022A (en) * 1961-03-24 1968-12-17 Ball Brothers Co Inc Etching composition and method
US3340188A (en) * 1962-08-23 1967-09-05 Phillips Petroleum Co Drilling fluid
US3356550A (en) * 1964-03-16 1967-12-05 Boeing Co Chemical milling of aluminum alloys
US3296142A (en) * 1964-04-06 1967-01-03 Ball Brothers Co Inc Etching composition and method of etching
US3412032A (en) * 1965-02-01 1968-11-19 Revere Copper & Brass Inc Etching bath composition
US3394060A (en) * 1965-02-19 1968-07-23 Ellwood S. Douglas Process for electrolytically regenerating ferric chloride etching solutions
US3376228A (en) * 1965-05-19 1968-04-02 Ball Brothers Co Inc Etching composition and method
US3330765A (en) * 1965-10-01 1967-07-11 Dow Chemical Co Powderless etching bath and method of etching
US3793053A (en) * 1966-05-10 1974-02-19 Owens Illinois Inc Glass decoration

Also Published As

Publication number Publication date
FR1189955A (fr) 1959-10-08
DE1071717B (enrdf_load_stackoverflow)

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