Badische Anilin & Soda Fabrik v. Kalle

94 F. 163, 1899 U.S. App. LEXIS 3056
CourtU.S. Circuit Court for the District of Southern New York
DecidedMay 8, 1899
StatusPublished
Cited by32 cases

This text of 94 F. 163 (Badische Anilin & Soda Fabrik v. Kalle) is published on Counsel Stack Legal Research, covering U.S. Circuit Court for the District of Southern New York primary law. Counsel Stack provides free access to over 12 million legal documents including statutes, case law, regulations, and constitutions.

Bluebook
Badische Anilin & Soda Fabrik v. Kalle, 94 F. 163, 1899 U.S. App. LEXIS 3056 (circtsdny 1899).

Opinion

COXE, District Judge.

This is an equity suit for the infringement of letters patent, No.- 524,254, granted August 7, 1894, to the complainant as assignee of Paul Julius, of Ludwigshafen, Germany, for improvements in the manufacture of blue coloring matter. The parts of the specification relied on by the complainant are as follows:

“The ultimate object of my invention consists in a new lake that may be produced as a pigment or upon fiber. It resembles vegetable indigo in color and fastness against washing and light so nearly as to form an artificial substitute for the same such as has been sought fdr many years by chemists. In arriving at this new lake I have made certain very essential intermediate discoveries or inventions which I also- desire to- secure by this patent. Thus I have discovered and recognized that a certain class of substances — (safranine-azo-naphthol bodies) — known as ‘insoluble precipitates’ and regarded as worthless bodies, can be rendered soluble, and then constitute a most valuable dye, and I have proved this discovery by rendering them soluble (as hereinafter further explained) and have hereby enriched the dyeing industry with a cheap dye of most excellent properties, the application of which is founded on transforming it into the above said lake. .* * * The compounds resulting from tL.o combination of the safranine-diazo compounds with the unsulphonated naphthols have been mentioned in chemical literature as insoluble precipitates. They could not be applied in the dyeing industry and have since been disregarded and fallen into the rank of useless bodies and were not included in the said German patent. * * * Make a one per cent, solution of safranine, taking one molecular proportion of the safranine used: say, about seven (7) parts of safranine T, or about six and three-fifths (6.6) parts of pheno-safranine, or about seven and seven-tenths (7.7) parts of dimethyl safranine. Diazotize by adding first a solution of sodium nitrite containing about one and four-tenths (1.4) parts of that salt, (one molecular proportion) and then twenty-three .(23) parts of hydrochloric acid containing about thirty-three per cent, real acid. (HG1). The solution during these operations must be kept cold with ice and stirred. Next run the mixture into an ice-cold solution of about three (3) parts of naphthol — either alpha or beta — (one molecular proportion) in about one hundred and sixty (160) parts of water and twenty-five (25) parts of caustic soda solution, containing about thirty-five per cent, of sodium hydrate (NaOH), stir the mixture thoroughly for several hours, then filter off the blackish violet precipitate of safranine-azo-naphthol thus formed. Now wash well with cold water, prolonging this until the liquor running off is deeply colored and shows that a soluble product has resulted. The paste then remaining [165]*165on the filter can be used in dyeing as such or after making up to a standard strength. Or without washing so thoroughly, my new dyestuff can also be prepared in the form of paste, (in which form it best meets the requirements of dyers) as follows: Stir the azo body, obtained as above described, with a little water and mix gradually with hydrochloric acid, until a test portion of the paste obtained is completely soluble in hot water. To prepare the new dyestuff from the quantities of safranine described in the above example, about two and one-fifth (2.2) parts of hydrochloric acid, containing about thirty-three per cent, of real hydrochloric acid (HC1) may be used at this stage of the process. The paste so obtained contains my new dyestuff in the form of a salt and can be diluted or made up to a standard strength. Instead of hydrochloric acid other acids may be used, such as acetic acid, sulphuric, nitric, oxalic, and tartaric acids, also salts which act as acids; but-of these hydrochloric and acetic acids give the best results. * * * My new dyestuff, however prepared, is a soluble safranine-azo-naphthol body. It occurs in the dry form and in paste, and forms a dark-colored powder with a slight metallic sheen giving a violet-black paste. It is soluble in both hot and cold wa ter giving violet to blue solutions, insoluble in alkalies, soluble in alcohol and practically insoluble or very slightly soluble in benzene. The dye can readily be recognized by iis behavior on treatment with reducing agents, for safranine and amido-naphthol occur in the reduction products. The dyestuffs which I desire to claim generically herein may be recognized as follows: If reduced with stannous chloride and hydrochloric acid, amido-naphthol is produced and can be recognized in any suitable well-known way. On careful and moderate reduction with zinc dust and acetic acid the safranine used in the production is regenerated and siiows the characteristic reactions of the members of the safranine series. * * 1
“I will now proceed to describe the new lake and the manner of obtaining it. *
“Example a.~ Eissolve about twenty parts of my new dyestuff in the form of powder (or the corresponding quantity of paste) in about two thousand parts of hot water; allow to cool. * * *
“Example, b. — To obtain the lake on cotton fiber proceed as follows: — Take the freshly boiled-out goods, pass them six times through a boiling-hot solution of sumac, and then leave them overnight in the liquid. Next wring out and pass about eight or ten times through a solution of antimony salt; wash well and wring out. Now fill the dye vat with the necessary quantity of water and add the amount of aluminium sulphate mentioned below, then enter the goods aud after passing them through the liquid once or twice, remove and wring them lightly by stretching. Add about one-eighth of the dye solution through a tine sieve, pass the goods again six times through the solution, then removing them and stretching as before add again one-eighth of the dye solution, subsequently add a quarter of the dye solution and finally the remainder thereof, manipulating in the same way. * * *
“The dyed goods are of a color resembling indigo, possess a degree of fastness to light and washing exceeding that obtainable with the ordinary aniline dyes and comparing advantageously with indigo itself. The coloring matter may be applied so' as not to bleed into the white.”

The claims in controversy are as follows:

“(1) As an article of manufacture a coloring matter lake resembling indigo in color, which can he obtained by combining a soluble safranine-azo-naphthol body with a. tanno-metallie mordant and which Is very fast to light and washing; upon suitable reduction it shows the reactions of safranine, upon treatment with caustic soda it shows the reactions of tannin and it contains a metal, substantially as described.
“(2) As an article of manufacture, the herein-described blue dyestuff which can be obtained from a safranine-azo-naphtliol and which may be recognized by the following characteristics: It is soluble in water, upon reduction with stannous chloride and hydrochloric acid, amido-naphthol is produced and upon reduction with zinc dust and acetic acid a safranine is produced, substantially as described.”
[166]*166“(4) The specific blue coloring matter (obtainable by rendering the safranine-azo-beta-naphthol hereinbefore mentioned soluble in water) which possesses the following characteristics: It is soluble in water, gives a blackish-green solution in sulphuric acid and on reduction gives alpha-amido-beta-naphtkol and safranine proper, all substantially as described.”

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Bluebook (online)
94 F. 163, 1899 U.S. App. LEXIS 3056, Counsel Stack Legal Research, https://law.counselstack.com/opinion/badische-anilin-soda-fabrik-v-kalle-circtsdny-1899.