US3296142A - Etching composition and method of etching - Google Patents

Etching composition and method of etching Download PDF

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Publication number
US3296142A
US3296142A US372053A US37205364A US3296142A US 3296142 A US3296142 A US 3296142A US 372053 A US372053 A US 372053A US 37205364 A US37205364 A US 37205364A US 3296142 A US3296142 A US 3296142A
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etching
weight
composition
castor oil
alkyl
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US372053A
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Sherer Abraham Isidor
Ruzicka John
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Ball Corp
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Ball Brothers Co
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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
    • 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

  • This invention relates to a novel etching composition and method and more particularly relates to a new and improved etching composition for use in the powderless etching of printing plates and relates to a novel method of powderless etching using such composition.
  • Patent No. 2,828,194 discloses an etching composition in which a sulfated castor oil is employed in combination with nitric acid and an organic liquid. This etching bath did not produce the degree of etching quality required by the printing industry, and in addition, was inconsistent, unpredictable and uncontrolled in its etching performance.
  • Patent No. 2,979,387 discloses an etching composition containing an alkyl aryl sulfonate in combination with nitric acid and an organic liquid. Plates etched with this composition also were not considered completely 'successful because of insufiicient depth of etch between the image surface and the recessed portions of the plate. Furthermore, if the proportion of the alkyl aryl sulfonate was changed in an attempt to achieve greater depth, undercutting of the image area resulted. Thus, alkyl aryl sulfonate etching compositions were also not commercially successful.
  • etching compositions heretofore employed it was completely unexpected and surprising to discover the new and improved etching composition and etching method of the present invention.
  • the smoothness of the shoulder and the speed of etching are substantially improved.
  • the etched image produced is not undercut but has an acceptable shoulder angle.
  • the etching composition of the invention provides greater flexibility in the formulation of the etching bath.
  • the etching composition of the present invention comprises a sulfated castor oil, an alkyl aryl sulfonate, a petroleum solvent and water. Prior to etching, the above composition is mixed with nitric acid and additional water to form the etching bath.
  • the sulfated castor oil employed in the etching composition of the invention advantageously has on a dry basis between about 6% and 9% by weight of organically combined S0 an acid value of between about 18% and 25% by weight calculated as oleic acid, and an alkalinity of between about 2.2% and 3% calculated as KOH.
  • the alkyl aryl sulfonate advantageously has an alkyl group with between about 10 and .12 carbon atoms.
  • Particularly useful for use in the etching composition of the present invention are alkyl benzene sulfonates, such as sodium dodecyl benzene sulfonate, sodium decyl benzene sulfonate, dodecyl benzene sulfonic acid, etc.
  • the petroleum solvent is advantageously an aromatic solvent, for example, Solvesso 150 sold by Esso Standard Oil Co., Modsol 52 sold by American Mineral Spirits Co., etc.
  • the proportion of the sulfated castor oil in the etching United States Patent 0 ice composition is advantageously between about 25 and 40% by weight and preferably between about 30% and 35%.
  • the alkyl aryl sulfonate is advantageously present in a percentage between about 0.3% and 2% by weight and preferably between about 0.9% and 1.2%.
  • the proportion of solvent is preferably between about 60% and 72% by weight and particularly between about 62% and 67%.
  • the remainder of the composition is advantageously water.
  • the above composition is mixed with nitric acid and water to form an etching bath containing, for example, between about 12% and 16% by weight of nitric acid, 0.6% and 1% of sulfated castor oil, 0.007% and 0.05% by weight of alkyl aryl sulfonate, 1.4% and 1.8% by weight of petroleum solvent and the remainder water.
  • the proportions of the above ingredients are respectively between 13% and 14.5%; 0.7% and 0.9%; 0.02% and 0.03%; and 1.5% and 1.6% by weight. Excellent results have been achieved when the ingredients have been used in approximately the proportions set forth in the following example:
  • Aromatic petroleum solvent (Aromatic content While solutions made according to the present invention can be used to good advantage in etching plates composed of a variety of metals, excellent results'have been achieved with zinc and magnesium alloys. Examples of such alloys are as follows:
  • Example I calculated as KOH), 0.025% dodecyl benzene sulfonic acid, and the remainder water, was formulated and used to etch a zinc alloy plate containing about 0.1% aluminum, 0.06% magnesium and less than about 0.005% of other metals. The etching was conducted for about 20 minutes and produced a depth of etch of about 0.04 inch, a half-tone depth of about 0.006 inch in 10% 65 screen half-tones and a bowl depth of about 0.015 inch. No undercutting of the images was observable upon inspection of the plate with a 10X magnifying glass.
  • Example II The procedure of this example was the same as that of Example 1, except that the sulfated castor oil mixture had an organically combined S content of about 8%, an acid value of about an alkalinity of about 2.4%. Also, 0.031% of dodecyl benzene sulfonic acid was employed.
  • the above description and examples show that the present invention provides a novel etching composition and etching method.
  • the etching composition of the invention provides a greater flexibility in bath formulations and permits the use of a wider range of sulfated castor oils. Furthermore, the etched image so produced has a smoother shoulder angle, and undercutting is eliminated. Moreover, the speed of etching is significantly faster.
  • An additive for an etching composition consisting essentially of between about and 40% by weight of a sulfated castor oil, between about 0.3% and 2% by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms,
  • An additive for an etching composition consisting essentially of between about and by Weight of a sulfated castor oil, between about 0.9% and 1.2%
  • An aqueous etching bath consisting essentially of between about 0.6% and 1% by Weight of a sulfated castor oil, between about 0.007% and 0.05% by weight Therefore, the invention is of an alkyl-benzene sulfonate the alkyl group containing between about 10 and 12 carbon atoms, between about 1.4% and 1.8% by weight of a petroleum solvent, between about 12% and 16% by weight of nitric acid, and water.
  • An aqueous etching bath consisting essentially. of between about 0.7% and 0.9% by weight of a sulfated castor oil, between about 0.02% and 0.03% by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms, between about 1.5% and 1.6% by weight of a petroleum solvent, between about 13% and 14.5% by weight of nitric'acid, and water.
  • sulfated castor oil between about 0.007% and 0.05%
  • a method of etching a metal plate having portions of its surface covered with an acid resistant coating to define a design which comprises applying to the surface of the plate an etching bath consisting essentially of between about 0.7% and 0.9% by weight of a sulfated castor oil, between about 0.02% and 0.03% by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms, between about 1.5 and 1.6% by weight of a petroleum solvent, between about 13% and 14.5% by weight of nitric acid, and water.

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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)

Description

3,296,142 ETCHING COMPOSITION AND METHOD OF ETCHING Abraham Isidor Sherer, Clifton, NJ., and John Ruzlcka,
Brooklyn, N.Y., assignors to Ball Brothers Company Inc., Muncie, Ind., a corporation of Indiana N Drawing. Filed Apr. 6, 1964, Ser. No. 372,053
14 Claims. (Cl. 252-794) This application is a continuation-in-part of application Serial No. 80,993, filed January 6, 1961, which in turn is a continuation-in-part of application Serial No. 688,826, filed October 8, 1957, now abandoned.
This invention relates to a novel etching composition and method and more particularly relates to a new and improved etching composition for use in the powderless etching of printing plates and relates to a novel method of powderless etching using such composition.
Various types of powderless etching compositions have been proposed in the past but none of the compositions previously suggested have proven to be completely successful. For example, Patent No. 2,828,194 discloses an etching composition in which a sulfated castor oil is employed in combination with nitric acid and an organic liquid. This etching bath did not produce the degree of etching quality required by the printing industry, and in addition, was inconsistent, unpredictable and uncontrolled in its etching performance.
Patent No. 2,979,387 discloses an etching composition containing an alkyl aryl sulfonate in combination with nitric acid and an organic liquid. Plates etched with this composition also were not considered completely 'successful because of insufiicient depth of etch between the image surface and the recessed portions of the plate. Furthermore, if the proportion of the alkyl aryl sulfonate was changed in an attempt to achieve greater depth, undercutting of the image area resulted. Thus, alkyl aryl sulfonate etching compositions were also not commercially successful.
In view of the above and other deficiencies and shortcomings of etching compositions heretofore employed, it was completely unexpected and surprising to discover the new and improved etching composition and etching method of the present invention. The smoothness of the shoulder and the speed of etching are substantially improved. Also, the etched image produced is not undercut but has an acceptable shoulder angle. Furthermore, the etching composition of the invention provides greater flexibility in the formulation of the etching bath.
The etching composition of the present invention comprises a sulfated castor oil, an alkyl aryl sulfonate, a petroleum solvent and water. Prior to etching, the above composition is mixed with nitric acid and additional water to form the etching bath.
The sulfated castor oil employed in the etching composition of the invention advantageously has on a dry basis between about 6% and 9% by weight of organically combined S0 an acid value of between about 18% and 25% by weight calculated as oleic acid, and an alkalinity of between about 2.2% and 3% calculated as KOH.
The alkyl aryl sulfonate advantageously has an alkyl group with between about 10 and .12 carbon atoms. Particularly useful for use in the etching composition of the present invention are alkyl benzene sulfonates, such as sodium dodecyl benzene sulfonate, sodium decyl benzene sulfonate, dodecyl benzene sulfonic acid, etc.
The petroleum solvent is advantageously an aromatic solvent, for example, Solvesso 150 sold by Esso Standard Oil Co., Modsol 52 sold by American Mineral Spirits Co., etc.
The proportion of the sulfated castor oil in the etching United States Patent 0 ice composition is advantageously between about 25 and 40% by weight and preferably between about 30% and 35%. The alkyl aryl sulfonate is advantageously present in a percentage between about 0.3% and 2% by weight and preferably between about 0.9% and 1.2%. The proportion of solvent is preferably between about 60% and 72% by weight and particularly between about 62% and 67%. The remainder of the composition is advantageously water.
The above composition is mixed with nitric acid and water to form an etching bath containing, for example, between about 12% and 16% by weight of nitric acid, 0.6% and 1% of sulfated castor oil, 0.007% and 0.05% by weight of alkyl aryl sulfonate, 1.4% and 1.8% by weight of petroleum solvent and the remainder water. Advantageously, the proportions of the above ingredients are respectively between 13% and 14.5%; 0.7% and 0.9%; 0.02% and 0.03%; and 1.5% and 1.6% by weight. Excellent results have been achieved when the ingredients have been used in approximately the proportions set forth in the following example:
Percent by volume 42 Baum nitric acid 13.8 Aromatic petroleum solvent (Aromatic content While solutions made according to the present invention can be used to good advantage in etching plates composed of a variety of metals, excellent results'have been achieved with zinc and magnesium alloys. Examples of such alloys are as follows:
A. Zinc-base alloys: I
(1) 0 to 1.0% cadium; 0 to 0.025% iron; 0 to 0.05% magnesium; 0 to 0.2% nickel; and remainder zinc;
(2) 0 to 1.0% aluminum; 0 to 0.05 magnesium; and remainder zinc; and
(3) At least 90% zinc and the remainder, other metals.
B. Magnesium-base alloys:
' (1) 3% aluminum; 1% zinc; 0.2% manganese; and remainder magnesium; and
(2) At least magnesium and the remainder, other metals.
The invention will be described in greater detail with reference to the following examples which are intended to be illustrative of the invention and not restrictive thereof. In the examples, parts and percentages are by weight.
Example I calculated as KOH), 0.025% dodecyl benzene sulfonic acid, and the remainder water, was formulated and used to etch a zinc alloy plate containing about 0.1% aluminum, 0.06% magnesium and less than about 0.005% of other metals. The etching was conducted for about 20 minutes and produced a depth of etch of about 0.04 inch, a half-tone depth of about 0.006 inch in 10% 65 screen half-tones and a bowl depth of about 0.015 inch. No undercutting of the images was observable upon inspection of the plate with a 10X magnifying glass.
In contrast, when using an etching bath in which the sulfated castor oil was omitted, severe undercutting occurred, yielding a plate completely unsatisfactory for printing.
The use of an etching bath similar to the bath of the invention but in which the alkyl aryl sulfonate was tory for printing.
Example II The procedure of this example was the same as that of Example 1, except that the sulfated castor oil mixture had an organically combined S content of about 8%, an acid value of about an alkalinity of about 2.4%. Also, 0.031% of dodecyl benzene sulfonic acid was employed.
The etched plates produced with the above bath exhibited the same superiority of etch shown by the plates produced with the bath of the invention in Example I.
The above description and examples show that the present invention provides a novel etching composition and etching method. The etching composition of the invention provides a greater flexibility in bath formulations and permits the use of a wider range of sulfated castor oils. Furthermore, the etched image so produced has a smoother shoulder angle, and undercutting is eliminated. Moreover, the speed of etching is significantly faster.
It will be apparent that various modifications in the composition and method described may be made within the scope of the invention. not intended to be limited to'the specific formulations and procedures set forth in detail herein except a may be required by the following claims.
What is claimed is:
1. An additive for an etching composition consisting essentially of between about and 40% by weight of a sulfated castor oil, between about 0.3% and 2% by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms,
and between about 60% and 72% by weight of a pctroleum solvent.
2. An additive for an etching composition consisting essentially of between about and by Weight of a sulfated castor oil, between about 0.9% and 1.2%
by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms, and between about 62% and 67% by weight of a pctroleum solvent.
3. An additive for an etching composition according to claim 1 in which the sulfated castor oil contains between about 6% and 9% by Weight on a dry basis of organically combined S0 and the solvent is an aromatic petroleum solvent.
4. An additive for an etching composition according to claim 1 in which the aromatic content of the solvent is about 90% and the flash point is about 150 F.
5. An additive for an etching composition according to claim 1 in which the alkyl-benzene sulfonate is sodium dodecyl benzene sulfonate.
6. An additive for an etching composition according to claim 1 in which the sulfated castor oil on a dry basis has an organically combined S0 content between about 6% and 9% by weight, an acid value between about 18% and 25% by weight calculated as oleic acid and an alkalinity between about 2.2% and 3% by weight calculated as KOH.
7. An aqueous etching bath consisting essentially of between about 0.6% and 1% by Weight of a sulfated castor oil, between about 0.007% and 0.05% by weight Therefore, the invention is of an alkyl-benzene sulfonate the alkyl group containing between about 10 and 12 carbon atoms, between about 1.4% and 1.8% by weight of a petroleum solvent, between about 12% and 16% by weight of nitric acid, and water.
8. An aqueous etching bath consisting essentially. of between about 0.7% and 0.9% by weight of a sulfated castor oil, between about 0.02% and 0.03% by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms, between about 1.5% and 1.6% by weight of a petroleum solvent, between about 13% and 14.5% by weight of nitric'acid, and water.
9. An aqueous etching bath according to claim 7 in which the sul'fated castor oil on a dry basis has anorganically combined S0 content between about 6% and 9% by weight, an acid value of between about 18% and 25% by weight calculated as oleic acid, and an alkalinity of between about 2.2% and 3% by weight calculated as KOH.
10. An aqueous etching bath according to claim 7 in which the alkyl-benzene sulfonate has an alkyl group containing between about 10 and 12 carbon atoms.
11. An aqueous etching bath according to claim 7 in which the alkyl-benzene sulfonate is sodium dodecyl benzene sulfonate.
12. A method of etching a metal plate having portions of its surface .covered with an acid resistant coat-.
sulfated castor oil, between about 0.007% and 0.05%
by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms, between about 1.4% and 1.8% by weight of a petroleum solvent, between about 12% and 16% by weight of nitric acid, and water.
13. A method of etching a metal plate having portions of its surface covered with an acid resistant coating to define a design which comprises applying to the surface of the plate an etching bath consisting essentially of between about 0.7% and 0.9% by weight of a sulfated castor oil, between about 0.02% and 0.03% by weight of an alkyl-benzene sulfonate having an alkyl group containing between about 10 and 12 carbon atoms, between about 1.5 and 1.6% by weight of a petroleum solvent, between about 13% and 14.5% by weight of nitric acid, and water.
14. A method of etchingaccording to claim 12 in which the sulfated castor oil on a dry basis ha an organically combined S0 content between. about 6% and 9% by weight, an acid value between about 18% and 25 by weight calculated as oleic acid, and an alkalinity of between about 2.2% and 3% by weight calculated as KOH. V
References Cited by the Examiner UNITED STATES PATENTS 2,828,194 3/1958 Hopkins et al. 25279.2 2,979,387 4/1961 Easely et al. 252-79.4 3,074,836 1/ 1963 Sherer et al. 156-18 SAMUEL H. BLECH, Primary Examiner.
ALBERT T. MEYERS, JULIUS GREENWALD, LEON D. ROSDOL, Examiners.
W. E. SCHULZ, Assistant Examiner.

Claims (1)

1. AN ADDITIVE FOR AN ETCHING COMPOSITION CONSISTING ESSENTIALLY OF BETWEEN ABOUT 25% AND 40% BY WEIGHT OF A SULFATED CASTOR OIL, BETWEEN ABOUT 0.3% AND 2% BY WEIGHT OF AN ALKYL-BENZENE SULFONATE HAVING AN ALKYL GROUP CONTAINING BETWEEN ABOUT 10 AND 12 CARBON ATOMS, AND BETWEEN ABOUT 60% AND 72% BY WEIGHT OF A PETROLEUM SOLVENT.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402083A (en) * 1965-06-16 1968-09-17 Master Etching Machine Company Powderless etching method for etching relief images in aluminum
US4246130A (en) * 1979-06-21 1981-01-20 Amchem Products, Inc. Stripping composition and method for metals
US20090084683A1 (en) * 2006-02-28 2009-04-02 Agfa Graphics Nv Method for making a lithographic printing plate support

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2828194A (en) * 1956-09-28 1958-03-25 Dow Chemical Co Etching
US2979387A (en) * 1956-08-27 1961-04-11 Dow Chemical Co Etching
US3074836A (en) * 1956-07-11 1963-01-22 Ball Brothers Co Inc Baths for one-stage quick etches

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074836A (en) * 1956-07-11 1963-01-22 Ball Brothers Co Inc Baths for one-stage quick etches
US2979387A (en) * 1956-08-27 1961-04-11 Dow Chemical Co Etching
US2828194A (en) * 1956-09-28 1958-03-25 Dow Chemical Co Etching

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402083A (en) * 1965-06-16 1968-09-17 Master Etching Machine Company Powderless etching method for etching relief images in aluminum
US4246130A (en) * 1979-06-21 1981-01-20 Amchem Products, Inc. Stripping composition and method for metals
US20090084683A1 (en) * 2006-02-28 2009-04-02 Agfa Graphics Nv Method for making a lithographic printing plate support

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