US2303477A - Tanning and dyeing leather - Google Patents

Description

Patented Dec. 1, 1942 oFrIcE IANNIN G AND DYEING LEATHER No Drawing. Application July 3, 1941, Serial No. 401,005

8 Claims.

-This invention relates to a process for the tanning and dyeing of leather. Heretofore leather has been customarily tanned and dyed in separate processes. In my invention the taming and dyeing of leather is carried out in a single process which produces a better leather and a better dyeing.

Although there are many points of particular novelty in my process, my process may be said to consist in general of partially tanning the skin. in a chrome tan bath containing sodium formate, dyeing the skin with an acid dye, and completing the chrome tanning of the leather. The term "acid dy is variously defined in the literature of the prior art, but in connection with my invention the acid dyes are described as watersoluble, non-basic dyestufls whose individual molecules contain at least one acid group such as --SOaX. OSOsX, -COOX, -COX, -SO2NXSQ2-, in which formulae X is hydro- :ien, alkali metal, ammonia or substituted ammonia. It is believed that this definition includes the classes called "acid dyes by the various authorities as well as certain classes not ordinarily considered acid by some authorities. The following dyestuffs are illustrative of those which are useful: Pontachrome Brown G (C. I. No.

238), Pontachrome Blue Black R Cone. (C. I. No. 202) ,Pontacyl Blue Black SX (C. I. No. 246) Pontacyl Brilliant Blue A (C. I. No. 714), Pontacyl Carmine SE (C. I. No. 57), Pontacyl Dark Green B (C. I. No. 247), Pontacyl Fast Black BBO (C. I. No. 307), Pontacyl Fast Blue SE (C. I. No. 289), Pontacyl Fast Violet 103 (C. I. No. 696) Pontacyl Green BL Conc. (C. I. No. 666), Pontacyl Navy Blue M4B (C. I. No. 304), Du Pont O an e II Cone. (C. -I. No. 151) Du Pont Orange R0 (C. I. No. 161), Du Pont Quinoline Yellow Cone. (C. I. No. 801), Pontamine Blue BB Supra Cone. (C. I. No. 406), Pontamine Blue RW (C. I. No. 512), Pontamine Brown DBGN (C. I. No. 596). Pontamine Diazo Black BHSW Cone. (C. I. No. 401), Pontamine Fast Red F (C. I. No. 419) Pontamine Fast Scarlet 4BS (C. I. No. 326), Pontamine Green Bx (C. I. No. 593), Pontamine Orange R (C. I. No. 415), Pontamine Sky Blue 53)! (C. I. No. 520), Pontamine Steel Blue G (C. I. No. 590), Pontamine Yellow CH (C. I. No. 365), Du Pont Resorcin Brown 5G (C. I. No. 234), Du Pont Stilbene Yellow G Conc. (C. I. No. 620), O-amino phenol resorcin; O-amino phenolresorcin, cop'pered; p-disulfanilamide 3 (p-cresol) 2, and p-amino salicylic acidresorcinol picramic acid.

5 including pickling in order to obtain optimum results so the process will be described as applied to a skin which has been pickled.

In one of the examples fleshing is carried out during my process, but it is frequently desirable to complete the fieshing prior to the commencement of the process.

The chromium salts which are used in my process are those which are customarily used in chrome tanning. Those which are listed in this 15 specification are merely exemplary. The sodium.

formate, whose use is referred to in the specification, is merely exemplary of the alkali metal salts of' organic acids such as sodium acetate and sodium lactate, sodium oxalate, sodium glycolate and sodium adipate, and the other alkali metal salts of these or other organic acids. In the literature these agents are called maskin agents or buiiering agents and their function in this process is to give; added penetration and shorten the time required in the process.

As apart of my invention I have devised a new method of preparing a tan bath which has considerable advantages. It involves, generally speaking, the boiling of the chrome tanning ma terial in a volume of water less than that which has heretofore been used, allowing the boiled tan bath to stand for some time, for instance, overnight, and extending by the addition of water. During the period of standing crystals tend to 35 form in the concentrated liquor, which dissolve easily on extension of the bath with water.

' The method of preparing the tan bath is illustrated by the followingexample:

108 pounds of commercial basic chromium sul- -fate are dissolved in 25 gallons of boiling water. pounds of solid sodium formate (or substitute) are added. The solution is boiled five minutes. It is allowed to cool and stand overnight. Crystals are formed in this liquor. extended to the order of gallons and heated to about 80 F. before use in the tan bath. The crystals are dissolved in this operation.

The following examples illustrate the invention. The quantities are by weight and they and the details of the process are illustrative, not limitative.

Example I Nine hundred pounds of bated domestic sheepskin which had been degreased and which had The liquor is been pickled with sulfuric acid and common salt and which had a pH value of about 2.0 as determined by spotting with a 0.04% solution of thymol blue were treated for minutes 'in a revolving tanning drum at a temperature of 80 F. with a solution prepared by dissolving 45 pounds of common salt in 20 gallons of water.

A tanning bath was prepared by boiling together in gallons of water 63 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CrzOa) and 31 pounds of sodium formate and allowing to stand and cool overnight. It was extended by the addition of 40 gallons of water and was admitted, after heating, through the hollow trunnion to the revolving drum containing the sheepskins. The sheepskins were allowed to drum in i the tanning bath at a temperature of 80 F. for

90 minutes, after which they had a pH value of about 3.8 as determined by spotting with an 0.04% solution of Bromphenol Blue.

An alternative method of preparing the tan bath was to boil the chromium sulfate and sodium formate in 40 gallons of water and cool to a temperature of 80 F., immediately injecting it into the tanning drum. This alternative method is not preferred.

A solution was prepared by dissolving 11 pounds of sodium bicarbonate in 10 gallons of water at 80 F., and poured through the hollow trunnion into. the revolving drum containing the partially tanned sheepskins, the drumming being continued at a temperature of 80 F. for 30 minutes. After that drumming period the partially tanned sheepskins had a pH value of about 4.5 as determined by spotting with an 0.04% solution of Bromcresol Green.

The partially tanned sheepskins were removed from the tanning drum and refleshed (excess adipose tissue being removed from the flesh sur-- faces of the skin in the process called shaving) Fleshing is usually completed before tanning begins, but in this process it is advantageous in the securing of optimum results to be sure that the adipose tissue is fleshed, partially-tanned sheepskins were returned to the tanning drum, which was fitted with a perforated door, and revolved, water at completely removed. The

minutes, the solid door was replaced by a perforated door, and the drum was revolved until the excess liquor had drained oil.

A tanning bath was prepared by boiling together in 6 gallons of water 27 pounds of com-v tinued at a temperature of 80 F. for 60 minutes.

80 F. being flowed through it for 15 minutes.

Excess liquor was drained from the drum, and the perforated door was replaced by a. solid door.

A dye bath. was prepared by boiling together in 30 gallons o1' water 36 pounds of a mixture of dyestufi's comprising parts of Pontamine Brown RMR (C. I. No. 420), 35 parts of Pentachrorne Brown RH Conc. (Mordant Acid dye, Pr. 5) 15 parts of Pontamine Brown NCR (C. I. No. 596) 10 parts of Pontamine Green S. Cone. (C. I. No. 583) and 5 parts of Pontacyl Fast Red AS Cone. (C. I. No. 176). The dyestufl solution was allowed to cool to 110 1F. A solution was prepared by dissolving in 30 gallons of water at 110 F. 36 pounds of quebracho tanning extract, and the two solutions were combined and added, in one addition through the hollow trunnion, to the revolving drum containing the rinsed, fleshed; partially tanned sheepskins, which were allowed to drum therein at a temperature of 110 F. for 30 minutes.

A solution was prepared by dissolving 9 pounds of muriatic acid (approximately 32% hydro- A solution was prepared by dissolving in 10 gallons of water at a temperature of F. 5 pounds of sodium bicarbonate, and added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, completelytanned sheepskins. The drumming was continued for 30 minutes at a temperature of 80 F., the solid door of the drum was replaced by a perforated door, water at a temperature of F. was allowed to flow through the revolving drum for 30 minutes, thetemperature of the rinsing waterwas raised to F. and the rinse was continued for 10 minutes.

An emulsion was prepared by stirring into 60 gallons of water at 140 F. 20 pounds of commercially prepared fatliquor (comprising approximately 65% sulfonated cod oil, 15% unsulfonated cod oil and 20% water), and added, in one addition through the hollow trunnion, to the rescaled revolving drum containing the rinsed, dyed, completely-tanned sheepskins. The drumming was continued for 30 minutes. The sheepskins were removed from the drum and horsed-up to drain.

The fatliquored, dyed, completely-tanned sheepskins were finished by methods known to be appropriate to the finishing of chrome tanned leather. 1

The leather prepared by this process may be used as chrome-tanned grain sheepskin garment leather. The usual methods employed in the preparation of this type of leather involve.

tained by either of the known general methods and produces it more economically. This leather is characterized by having a higher tensile strength, a. full, round, soft anduniform feel, and a full, level and fast brown color. The higher tensile strength is evidenced in the markedly decreased number of tear offs in the subsequent staking operation. This reduction. of tear offs represents an economy by the reduction of damage to the leather in processing. A fuller shade is obtained by this method than by the methods that involve fatliquoring, drying, and rewetting before dyeing. A more level shade of color is obtained by my method. A more uniform color is obtained among the various skins of a, group than among a similar group prepared by the known methods. There is a marked reduction of darker colored imperfections on the grain of the skins. The color is faster to washin The percentage of first grade grain sheepskin garment leather usually prepared from low grade domestic sheepskins by the known methods is normally approximately The percentage of first grade leather produced by this example is increased to approximately 15%. The percentage of low grade leather is reduced markedly. The

improved leather characteristics represent a marked increase in value.

. A decided economy in time, equipment and expense is effected by this invention since a dyed leather having superior properties can be prepared. in less than one-half the normal time required for the known process involving dyeing after crusting (drying). My process is faster than either of the prior processes briefly described above. v

A known method of preparing leather included basic chromium salts and an organic acid salt in the tan bath, and dyed after tanning, or after crusting and rewetting.

The shade of the dyed leather obtained by the method of the example has superior levelness, fastness, and uniformity compared to the shade obtained by the said prior process. The uniformity from skin'to skin, the roundness, softness, and uniformity of the leather are also 'improved.

This process is not to be confused with the a older and inferior process of tanning completely,

dyeing, and retaining.

The physical characteristics of the leather pre-.-.

pared by this and other examples may be altered by varying the amount and kind of organic acid alkali metal salt used in either of the tanning baths. For example, if 50 pounds of sodium formate are used in the first bath, the resulting leather will be plumper and softer than that resulting from the use of 31 pounds of sodium formate. If 25 pounds of sodium formate are used, the resulting leather will be thinner and boardier than if 31 pounds are used. Corresponding alterations in the physical characteristics of the leather may be obtained by varying the amount of masking agent used in the second tanning bath. The sodium formate used in either or both tanning baths may be replaced by varying amounts of other alkali metal salts ,of organic acids, such as sodium acetate, or lactate or oxalate, etc., or mixtures of them, with consequent-variation in leather properties.

Alterations in the physical characteristics of the leather may also be obtained by varying the amount of whatever chromium salt is used in the tanning baths. Increased amounts of chromium salt will produce softer, fuller leather.

In Example I 4% (on the shaved weight of the pickled sheepskin) of quebracho tanning extract is included in the dyebath. The inclusion of quebracho tanning extract helps to impart a full, soft, round feel to the leather. The amount of quebracho tanning extract may be raised as high as 12% (on the shaved weight of pickled sheepskin), or it may be omitted from the dyebath. Varying degrees of softness, fullness and roundness of feel may be obtained by varying the amount of quebracho tanning extract. Instead of quebracho tanning extract. natural tanning extracts may be included in the dyebath with a change in result. For instance.

- if hemlock tanning extract is substituted for quebracho tanning extract (on a part-fcr-part basis), firmer, less plump, less round feeling leather will be obtained. Amounts of extract from 012% on the shaved weight of pickled sheepskin produce useful results. Examples of useful extracts are quebracho, hemlock, sumac, gambler, logwood, divi-divi, oak bark, mangrove, wattle bark, spruce bark, and valonia. They are used alone or in combination. The inclusion of vegetable tanning extracts in the dyebath is not necessary for the operation of the examples, but

. their inclusion frequently produces useful characteristics in the leather. Synthetic tanning agents may be included in the dyebath in addition to, or instead of, vegetable tanning extract. For instance, from 0-5% of the following of synthetic tanning agents may be included: sulfite cellulose waste liquor, sulfonated'phenol-formaidehyde condensates or sulfonated cresol formaldehyde condensates.

The dyebath used in Example I contained 4% (on the shaved weight of pickled sheepskin) of a mixture of synthetic dyestuffs. The amount of dyestuff may be altered to obtain various depths of color.

The dyestuffs, when applied according to the foregoing directions, ailix themselves principally to the grain and flesh surfaces of the skins, there being only slight penetration of the color to the interior of the skins, but the extent of penetration of color may be controlled by adjusting the pH value of the partially-tanned sheepskins prior to application of the dyestufis. If, in Example I, the pH is adjusted to pH 5.5 before application of the dyestuffs, partial penetration of color into the interior of the skins will be obtained. If thepH value is adjusted to pH 7.0

before application of the dyestuffs, full penetration of color into the interior of the skins will be obtained. The alkali used to adjust the pH value of the partially-tanned sheepskins need not be limited to sodium bicarbonate. Other alkalis,

for example sodium hydroxide, sodium carbonate,

sodium borate, ammonium hydroxide, disodium phosphate and trisodium phosphate, may be used. The use of disodium phosphate and trisodium phosphate to adjust the pH value is not preferred, because the phosphate ion is considered to have a harmful secondary effect on the leather. If the pH value of the partially-tanned sheepskins is adjusted to a value higher than pH 4.5, a correspondingly larger amount of muriatic acid should be used to exhaust the dyebath. Consequently, the amount of alkali used to set" the tannage after application of the second tanning bath should be increased. The acid used to exhaust the dyebath need not be limited to muriatic acid. Other inorganic and organic acids may be used. For example, sulfuric acid, formic acid and acetic acid.

The fatliquor used to treat the completelytanned leather need not be limited to one having the composition mentioned in Example I. Other fatliquors suitable for treating chrome-tanned grain garment leather prepared by known methods may be used.

Example I! Nine hundred pounds of domestic sheepskins which have been treated in the beam house for the manufacture of glove leather and which have been pickled with sulfuric acid and common salt and which have a pH value of about 2.0 as determined by spotting with an 0.04% solution of 'I'hymol Blue, are treated in a revolving tanning drum for 10 minutes with a solution prepared by dissolving 45 pounds of common salt in 20 gallons of water.

A tanning bath is prepared by boiling together in 14 gallons of water 60 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CraOa) and 32 pounds of sodium glycolate and allowing the resulting solution to stand overnight. It is extended with 50 gallons of water, heated at 80 F. and poured through the hollow trunnion into the revolving drum containing the sheepskins. The sheepskins are allowed to drum in the tanning bath at a temperature of 80 F. for 90 minutes. The solid door of the drum is replaced by a perforated door. The drum is revolved. Water at a temperature of 100 F. is allowed to flow through the revolving drum for 30 minutes. The partially tanned sheepskins are removed from the drum and horsed up to drain.

A dye solution is prepared by boiling 8 pounds of Pontamine Black E Double (C. I. No. 581) in 60 gallons of water and allowing the resulting solution to cool to 100 F. The drained, partially tanned sheepskins are spread on a dyeing table with their grain surfaces uppermost. The dye solution is brushed onto the grain surfaces. and the dyestufl is set by brushing the dyed surfaces with a 1% solution of hydrochloric acid. The dyed surfaces of the sheepskins are rinsed with water at a temperature of 100 F. The dyed, partialLv tanned sheepskins are returned to the tanning drum.

A tanning bath is prepared by boiling together in 7 gallons of water 30 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CrzOa) and 16 pounds of sodium glycolate and allowing the resulting solution to cool. The bath thus prepared is extended after the formation of crystals with 50 gallons of water and added through the hollow trunnion, to the revolving drum containing the dyed, partially tanned sheepskins. The sheepskins are allowed to drum in the tanning bath at a temperature of 80 F. for 60 minutes.

A solution is prepared by dissolving 8 pounds of sodium bicarbonate in 10 gallons of water at a temperature of 80 F. This solution is added,

in one addition through the hollow trunnion, to

the revolving drum containing the dyed, fully tanned sheepskins. The drumming is continued for 30 minutes at a temperature of 80 F. The solid door of the drum is replaced by a perforated door. The.drum is revolved. Water at a temperature of 100 F. is allowed to flow through the revolving drum for 20 minutes. The temperature of the rinsing water is raised to 130 F. and the rinse is continued or '10 minutes. The perforated door is replaced b a solid door.

An emulsion is prepared by stirring into 60 gallons of water at a tem rature of 140 F. 63 pounds of a commercially prepared fatliquor (comprising approximately 140% sulfonated cod oil, 30% unsulfonated neat's foot oil and 30% water). This emulsion is added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, fully-tanned sheepskins. The drumming is continued for 30 minutes at a temperature of 130 F.

The fatliquored, dyed, fully tanned sheepskins are removed from the drum and horsed-up to drain.

The leather prepared by this process may be used in the preparation of white-backed'glove leather. leveler black shade which is faster'to washing It is characterized by having a..fuller,-,

and a superior round, soft, uniform feel as compared to glove leather prepared by the known methods.

Example III Nine hundred pounds of bated domestic sheepskins which have been degreased and which have been pickled with sulfuric acid and common salt and which have a pH value of about 2.0 are treated in a revolving tanning drum for 10 minutes at a temperature of F., with a solution prepared by dissolving 45 pounds of common salt in 20 gallons of water.

A tanning bath is prepared by boiling together in 15 gallons of water 63 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CraOs) and 27 pounds of sodium oxalate and allowing the resulting solution to cool overnight. The bath thus prepared is extended with 40 gallons of water and added, in one addition through the hollow trunnion. to the revolving drum containing the sheepskins. The sheepskins are allowed to drum in the tanning bath at a temperature of 80 F. for minutes. After this drumming period the sheepskins have a pH value of about 3.5 as determined with Bromphenol Blue.

A solution is prepared by dissolving 15 pounds of sodium bicarbonate in 10 gallons of water at 80 F. This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the partially tanned sheepskins,

and the drumming is continued for 30 minutes at a temperature of 80 F. After this drumming period the skins have a pH value of about 5.0 as determined with Bromcresol Green.

The solid door of the drum is replaced by a perforated door. The drum is allowed to revolve. Water at a temperature of 80 F. is allowed to flow through the revolving drum containing the partially tanned sheepskins for 15 minutes. Excess liquor is drained from the drum and the perforated door is replaced by a solid door.

A solution is prepared by dissolving 45 pounds of hemlock tanning extract in 30 gallons oi water V at a temperature of F. and mixing'with a solution prepared by dissolving 30 pounds of Pontamine Brown RMR (C. I. No. 420) in 30 gallons of boiling water. This combined solution is cooled to a temperature of 100 F. and added in one addition through the hollow trunnion, to the revolving drum containing the partially tanned sheepskins. The drumming is continued at a temperature of 100 F. for 30 minutes. A solution prepared by adding 9 pounds of muriatlc acid (approximately 32% hydrochloric acid) to 10 gallons of water at a temperature of 80 F. is added to the drum. The drumming is continued for 15 minutes. The solid door of the drlmi is replaced by a perforated door. The drum is revolved. Water at a temperature of 100 F. is allowed to flow through the revolving drum for 30 minutes. The perforated door is replaced by a solid door.

A solution is prepared by dissolving '9 pounds of du Pont Basic Brown BR (C. I. No. 332) and 4 pounds of formic acid (87%) in 60 gallons of water at 100 F. This solution constitutes the dyebath. The dyebath is added, in one addition through the hollow trunnion, to the revolving drum containing the partially-tanned sheepskins; The drumming is continued at a temperature of 100 F. for 30 minutes. The solid door is replaced by a perforated door, and the drum is allowed to revolve. Water at a temperature of 100 F. is allowed to flow through the revolving drum for 30 minutes. The perforated door is replaced by a solid door.

'A solution is prepared by dissolving 45 pounds of hemlock tanning extract in 30 gallons of water at a temperature of 100 F. and mixing with a solution prepared by dissolving 30 pounds of Pontamine Brown RMR (C. I. No. 420) in 30 gallons of boiling water. This combined solution is cooled to a temperature of 100 F. and added in one addition through the hollow trunnion, to the revolving drum containing the partially tanned sheepslnns. The drumming is continued at a .temperature of 100 F. for 30 minutes. A solution prepared by adding9 pounds of muriatic I acid (approximately 32% hydrochloric acid) to 10 gallons of water at a temperature of 80 F. is i added to the drum. The drumming is continued for minutes. The solid door of the drum is replaced by a perforated vdoor. The drum is revolved. Water at a temperature of 100 F. is allowed to flow through the revolving drum for 80 minutes. The perforated door is replaced by a solid door.

A solution is prepared by dissolving 9 pounds of Du Pont Basic Brown BR (C. I. No. 332) and} pounds of formic acid (87%) in 60 gallons of water at 100 F. This solution constitutes the I dyebath. The dyebath is added, in one addition through the hollow trunnion, to the revolving drum containing the partially-tanned sheep skins. The drumming is continued at a temperature of 100 F. for 30 minutes. The solid door is replaced by a perforated door, and the drum is allowed to revolve. Water at a temperature of 100 F. is allowed to flow through the revolving drum for 30 minutes. The perforated door is replaced by a solid door.

in preparing chrome tanned grain sheepskin garment leather. It is characterized by having a leveler and fuller brown shade which is faster to washing and a plumper, fuller, frounder" feel than garment leather prepared by the known methods of completely tanning and dyeing; or tanning fatliquoring, crusting, rewetting and dyeing.

Example 1V Five hundred pounds of South American sheepskins which have been treated in the beam-house for the'manufacture of glove leather and which have been pickled with sulfuric acid and common salt and which have a pH value of about 2.2 as determined by spotting with an 0.04% solution of Thymol Blue are treated for 10 minutes in a revolving tanning drum with a solution prepared by dissolving 25 pounds of common salt in 12 gallons of water at a temperature of 80 F. 1

A tanning bath is prepared by boiling together in 9 gallons of water 40 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CraOs) and 13 pounds of sodium adipate and allowing the solution to stand overnight. The tanning bath thus prepared is extended with 25 gallons of water and added, in one addition through the hollow trunnion, to the revolving drum containing the sheepskins. The drumming is continued at a temperature of 80 F. for 90 minutes.

A solution is prepared by dissolving 4 pounds 2 of sodium carbonate in 5 gallons of water at a A tanning bath is prepared by boiling together I in 6 gallons of water 27 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CrzOa) and 13 pounds of sodium oxalate and allowing the resulting solution to stand. After crystal formation and extension with gallons of water the bath is poured into the revolving drum containing the partially tanned, dyed sheepskins. The drumtemperature of 80 F. This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the partially-tanned sheepskins. The drumming is continued, at a temperature of 80 F. for 30 minutes. The solid door of the drum is replaced by a perforated door. The drum is allowed to revolve. Water at a temperature of 100; F. is allowed to flow through the revolving drum for 30 minutes. The temperature of thevrinsin'g water is raised to 120 F. and the rinseis continued for 30 minutes. Excess liquor is allowed to drain from the drum,

ming is continued at a temperature of 80 F. for

minutes.

A solution is prepared by dissolving 5 pounds of sodium bicarbonate. in 10 gallons of water at 80 F. This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, completely tanned sheepskins. The drumming .is continued at a temperature of 80 F. for 30 minutes. The solid door of the'drum is replaced by a perforated door, and water at a temperature of 100 F. is allowed to flow through the revolving drum for 30 minutes. The temperature of the rinsing water is raised to 120 F., and the rinse is continued for 10 minutes. A An emulsion is prepared by stirring into 60 gallons of water at a temperature of 120 F. 30 pounds of a partially sulfonated cod oil (comprising approximately sulfonated cod oil, 15% unsulfonated cod oil and 20% water). This emulsion constitutes the flatliquor. The fatliqnor is added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, fully-tanned sheepskins. The drumming is and the perforated door is replaced by a solid oor.

A solution is prepared by boiling in 35 gallons of water 15 pounds of the synthetic dyestufi-- Pontachrome Brown G (C. 1.,No. 238). The solution is allowed to cool to a temperature of 120 F. and is then added, in one addition through the hollow trunnion, to the revolving drum containing the partially tanned sheepskins. The drumming is continued-at a temperature of 120 F. for 30 minutes.

A solution is prepared by adding 5 pounds of formic acid (approximately 87%) to 5 gallons of water at a temperature of 120 F. This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, partially-tanned sheepskins. The drumming is continued for 20 minutes. The solid door of the drum is replaced by a perforated door, and the drum is revolved until the excess liquor has drained mim the skins.

A tanning bath is prepared by boiling together in 4,5 gallons of water 20 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as Cr203) and 6.5 pounds of sodium .adipate and allowing the solu tion to cool to a temperature of 80 F. This tanning bath is added, after extension with 25 gallons of water, to the revolving drum containing prepared by this process may be used the dyed, partially-tanned sheepskins.v The drumming is continued at a temperature of 80 hemlock tanning extract and 20 pounds of sumac F. for 60 minutes. tanning extract. The dyestuff solution and tan A solution is prepared by dissolving 6 pounds ning extract solution are combined and added, in of sodium carbonate in gallons of water at a One addition through the hollow trunnion, to the temperature of 80 This solution is added, 5 revolving drum containing the partially-tanned in one addition through the hollow trunnion, to goatskins. The drumming is continued at a temthe revolving drum containing the dyed, iullyperature of 120 F. for 30 minutes. tanned sheepskins. The drumming is continued A solution is prepared by adding to 10 gallons for 30 minutes. The solid door of the drum is of water at a temperature of 120 F. 10 pounds replaced by a perforated door, and the drum is 10 of muriatic acid (approximately 32% hydroallowed to revolve. Water at a temperature of chloric acid). This solution is slowly added 100 F. is allowed to flow through the revolving through the hollow trunnion to the revolvin .drum for 30 minutes. The temperature of the drum containing the dyed, partially-tanned goatrinsing water is raised to 140 F. and the rinse skins. The drumming is continued ata temperais continued for 10 minutes. The perforated door ture of 120 F. for 30 minutes. The solid door of of the drum is replaced by a solid door. the drum is replaced by a perforated door. The An emulsion is prepared by stirring into 35 galdrum is revolved until the excess liquor has Ions of water at 140 F. 18 pounds of commerdrained from the skins. The perforated door is cially prepared fatliquor (comprising approxireplaced by a solid door. mately 65% sulfonated cod oil, 15% unsulfonated 2 A tanningbath is prepared by boiling together cod oil and 20% water). This emulsion is added. in 4 gallons of water l8pounds of commercially in one addition through the hollow trunnion, to prepared basic chromium sulfate (containing 'the revolving drum containing the dyed. 'fully- 23.2%"of' chromium calculated as CrzOs) and 9 tanned s eeps i e drumming is co i ed pounds of sodium acetate and allowing the solufor 30 minutes.- The fatliquored, dyed, fullytion to standuntil crystals form. 40 gallons of tanned sheepskins are removed from. the drum water are added, and the solution is poured into and horsed-up to drain. the revolving. drum containing the dyed, par- T ea r Dreparedby this example may be tially-tanned goatskins. The drumming is conused as chrome-tanned grain glove leather. It is tinued at a temperature of 80' F. for 60 minutes. characterized by having a ll r nd r. Softer. A solution is prepared by dissolving in 10 gal silkier feel, a leveler tan color which is faster to Ions of water ata temperature of 80 F. 7 pounds washing and a grain surface with less evidence of of sodium bicarbonate. This solution is added, in

imperfections than Elm/9193151161 P ep ed by e one addition through the hollow trunnion, to the known methods of manufacture. K revolving drum containing the dyed, completely- Example. V 5 tanned goatskins. The drumming is continued at a temperature of 80 F. for 30 minutes. The

Nine hundred pounds of Persian goatskins solid 01 t um is replaced by a perforated which have been processed in the beam house for doom The drum is revo1ve water at a g the manufacture of Sueded leather and Winch perature of 100 F. is allowed to flow through the have been pickled with sulfuric acid and common 40 dnnn for 20 minutes, The temperature of th salt and which'have a pH value 0 about rinsing water is raised to 140 F. and the rinse treated in a revolving tanning drum at e is -continued for 10 minutes. Excess liquor is Dent r 0 for 10 minutes with l on drained from the drum, and the perforated door prepared by dissolvin po of mm a [replaced by a solid door.

11120 8811131801 Wflter- 'Aniemulsion is prepared by stirring into A tannin bath is prepared by boiling toge r none of water at a temperature of 140 F. 45 in 12.5 gallons Of Wate 5 P0111155 01 unds-of commercially prepared fatliquor (comcially prepared basic chromium sulfate (containe f approximately 0% suuonated cod 11, 1 8 2 f chromium calculated ch03) n 20%unsulfonated neats foot oil and 50% water). 30 pounds or sodi acetate and allowing the This emulsion is added in one addition through solution to stand overnight. After extension with hollow trunnion, to the revolving drum 4088110118 01 water, bath is added to the ret mi g th dyed completely-tanned goatskins V01V1n8 drum n s, the goatskins' The The drumming is continued for 30 minutes. drum in 1 continued minutes at a The fatliquored, dyed, completely-tanned goatperature of 80 F. B' -skins are removed from the drum and horsed-up A solution is p e y dissolving in 10 to drain. The drained leather is' dried'ina drylons of water a a temperature 1 10 Pounds ing-tunnel. After it has become thoroughly dry, of sodium bicarb n This Solution 15 added" the leather is moistened in'damp sawdust and in one addition through the hollow trunnion, to bunem the revolving dr containing the Partially- Leather prepared by this process may be used tanned goatskins. The drum is continufid in preparing sueded chrome-tanned goatskin for- 30 minutes at a temperature of The leather. It is characterized by a level brown solid door of the drum is replaced by a perforated color and a, plump, full, round feeL' Sueded d r. The drum is revolved. Water at a goatskin leather prepared by orthodox chrome- D n re 0! 10 F. is llowed to flow through the tanning methods is pearled" (a term describing revolving drum for 30 minutes. treatment with materials such as flour and egg T e P a ly-mulled goats e removed y crusted, (dried) and wet-back before it from the drum, "wet-wheeled" (buffed) and reis dyed. These operations consume several days. turned tothe drum. Y e m t od of s ex p e these time-con A solution is prepared by boiling in 30 gallons 7o suming operations are eliminated. The shade is of water 63 pounds of the sy thetic dyestufi: lei/e119! than normally ed by the orthodox Pontamine Brown RMR'Conc. .(0. I. .No. 420). .methsd- The dyestufl solution is allowed to cool to a temx mple VI perature f 120 F. A solutionisprepfied by Two hundred pounds of drained, shaved Persian dissolving in 30 gallons of water 25 pounds of kidskins which have been pickled with sulfuric acid and common salt and which have a pH value of about 2.0 are treated for minutes at a temperature of 80 F. in a revolving tanning drum with a solution prepared by dissolving 10 lbs. of common salt in 4 gallons of water.

A tanning bath is prepared by boiling together in 3.75 gallons of water 16 pounds of commercially prepared basic chromium sulfate (containing 23.2% chromium calculated as C'rzOs) and 9.5 pounds of sodium formate and allowing the. resulting solution to stand. The oath thus prepared is extended with 22 gallons of water and added, in one addition through the hollow trun nion, to the revolving drum containing the kidskins. The kidskins are allowed to drum in the tanning bath at a temperature oi80' F. for 90 minutes. At the end of this drumming period the kidskins have a pH value of about 4.2..

Asolution is prepared by dissolving ounces of sodium bicarbonate in one gallon of water at a temperatureof .80 F. solution is added, in one addition through theholl-ow trunnion, to

' the revolving drum containing the partially tanned kidskins. The partially-tanned kidskins are allowedf to drum in the sodium-bicarbonate solution at a temperature of 580. F. for 15. minutes. A solution is made by dissolvingl 20 ounces of sodium bicarbonate in one gallon of water at a temperature of 80 solution'iis, added, in one addition through the hollow trunniomto the revolving drum containing .the -partiallytanned kidskins. are allowed to drum in the sodium bicarbonate solution for 25 minutes at a temperature of 80 F.

The solid door of the drum by a perforated door.

The partially-taniied kidskins is loosened and the excess liquor is allowed to drain from the.

drum. The solid door of the drum is replaced" Fifty gallons of water v at 80 F. are added to the drum through the.

hollow trunnion. The drum is revolved for five minutes to allow the excess liquor to drain from the partially-tanned kidskins.

A solution is made by dissolving 20 fluid ounces of commercial ammonium hydroxide (approximately 35%) in 4 gallons of water at 100 F.

This solution is added, in one addition through revolvingdrum containing the dyed, partiallythe hollow'trunnion, to the revolving drum con- I taining the partially-tanned kidsklns. Thepartially-tanned kidskins are drummed in the ammonia solution for three minutes at a teirlperature of 100 F.

A solution is prepared by boiling togetheriin 20 1 gallons of water the following synthetic dyestufls v pounds 12 ounces of du Pont Resorein Brown 5 (C. I. No. 234) 2.5 ounces of PontamineGreen S Conc. (C. I. No. 583), 6.5 ounces of Pontaniine' Green BX (C. I. No. 593), 5.2 ounces of Pc-ntamine Brown NCR (C. I. 596), 13 ounces of Pontamine The partia-lly tann'ed'v kidskins are drummed in the dyebath for '40 minutes at a temperature of 100 the hollow trunnion to the revolving drum containing the dyed, partially-tannedkidskins. The

drumming is continued for 15 minutes at a tern perature of 80 F.

The solid door of the drum is replaced by-a perforated door and the drum is revolved for.

three minutes. The perforated door is replaced bYa solid door.

A tanning bath is prepared by boiling together in 2 gallons of water 8 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CEO!) and 4 pounds 13 ounces of sodium formate and allowing the resulting solution to stand. This tanning is extended with 18 gallons of water and added, in one addition through the hollow $11111 nion, to the revolving drum containing the dyed. partially-tanned kidskins. The drumming is continued for minutes at a temperature of ,A solution, is prepared by dissolving 14.5 ounces (avoin) of sodium bicarbonate (NaHCOa) f in .2 gallons of water at 80 F. This solution is' added, in one addition through the hollow trunnion, to the revolving drum containing the dyed,

fully-tanned kidskins. The drumming is continued for 15 minutes at a temperature of 80 F. A

solution is prepared by dissolving 14.5 ounces- (avoin) of sodium bicarbonate in 2 gallons of water at80 F. This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, fully-tanned I kidskins The drumming is continued for-25 I minutes. The door of the drum is removed and :--the excess liquor is allowed to drain from the skins. .The drum Water; at 80 F. is allowed to how through the tannedkidsklns for 20 minutes. The temperature of the rinsing water is raised to F..- and the rinse is continued for 2 0 minutes.

of commercially prepared sulfonated cod oil into 18 gallons of water at 130 F. This emulsion constltutes the fatliquor. The fatliquor is added, in. oneaddition through the hollow trunnion, to

the revolving-drum containing the rinsed, dyed, fully-tanned kidskins. The drumming is con- -tinued for 30 minutes at a temperature'pf 130 F. The kidskins are removed from the drum and horsed-u'p to drain. H

The fully-tanned, dyed; iatliguored 'lridskins are dried, dampened, dry'kmilied, staked, tacked- I this process is characterized by a fuller, soften rounder feel andiaduller, leveler brown color j out and finished by known methods. 60-

'-The kidskihs treated' 'by'this process maybe used for chrome-tanned grain kidskin shoe upper leather. :The leather'prepared according to which is iasteri'to nwashing than dyed leather prepared by the-known methods of completely been degreas'ed and which have been pickled with sulfuric acid "and; common salt are treated in A solutionisfprepared by dissolving '32 fluid n a revolving tanning for 10 minutes with H01) in fourgallons of water at a temperature of 80 F. This solution is slowly added through is fitted with a perforated door.

' The per forated door is replaced by a solid door. An emulsion is prepared by stirring 3 pounds a solution prepared by dissolving 2.5 pounds of common salt in one gallon of water at a temperature of 80 F.

A tanning bath is prepared by boiling together in .75 gallon of water 2.5 pounds of commer- E, and the rinse is continued for 10 minutes. Excess liquor is allowed to drain from the drum.

,The perforated door of the drum is replaced by ,a solid door.

cially prepared basic chromium sulfate (containing 23.2% of chromium calculated asCreOs), 10 ounces of sodium acetate and 10 ounces of sodium lactate and allowing the solution to cool. After extension with 3 gallons of water, the tanning bath is added, in one addition through the hollow trunnion, to the revolving drum containing to drain.

Leather prepared The solid door of the drum is replaced by a Y perforated door. The drumis revolved. 'Water.

at a temperature of 100 F. is allowed to flow through the revolving drum containing the partially-tanned peccary skins for 20 minutes. The

temperature of the rinsing water is raised to 120 F. and the rinse is continued for 10 minutes. The excess liquor is drained from the'jdrum, and the perforated door is replaced byia solid door.

A solution is prepared by boiling together in 8 gallons of water 12 ounces of sodium bicarbonate, 8 ounces of Pontachrome Brown G (C. I. No. 238) and 2' ouncesof Pontachrome vBrown RH Gone. (a mordant acid dyestufl) This soiu-' tion constitutes the dyebath. The dyebath at atemperature of 110 F. is added, in one addition through the hollow trunnion, to the revolving drum, containing the partially-tanned peccary skins. The drumming is continued at a temperature of- 110' F. for minutes.

A solution is prepared by dissolving 12 oun of muriatic acid (approximately 32% 1101) in onewhalf gallon of water at 80% I". This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, partially tanned peccary skins. The drumming is continued for 20 minutes at a temperature of v80 F. The solid door of the drum is replaced by a perforated door and the excess liquor is allowed to drain from the drum. The perforated dooris replaced by a solid door. A tanning bath is prepared by boiling together in .5 gallon of water 1.5 pounds of commercially prepared basic chromium sulfate (containin 23.2% chromium calculated as CrsOa) 7 ounces of sodium acetate and 7 ounces ofsodium lac-' tate and allowing the solution to stand several hours. The tanning bath with 2.5 gallons of water added, is poured through the hollow trunnion into the revolving drum containing the dyed, partially-tanned peccary skins. The drumming is continued for 60 minutes at a temperature of 100 F.

A solution is prepared by dissolving 5 ounces of sodium bicarbonate in one-half gallon of water at a temperature of 80 F. This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the dyed, fully-tanned peccary skins. The drumming is continued for 30 minutes at a temperature of 80 F. The solid door of the drum is replaced by a perforated door. Water at a temperature of: 110 F. is allowed to flow through the revolving drum containing the dyed, fullytanned peccary skins for 20 minutes. The tem- An emulsion is'prepared by stirring into 2 gallons of water at 140 F. 3 pounds of commercially prepared fatliquor (comprising approximately 40% sulfonated cod oil, 30% unsulfonated neats foot oil-and 30% water. This emulsion is added, in one-addition through the hollow trunnion, to the revolving drum containing the dyed, fully-tanned peccary skins. The drumming is continued for 30 minutes at a temperature'of 140 F.

The fatliquored, dyed, fully-tanned peccary skins are removed from the drum and horsed-up by this process may be used for chrome-tanned grain pigskin glove leather. The time required for preparing dyed leather by this process is less than one-half that required by the known process 'of completely tanning and subsequently dyeing. The dyed leather has a fuller, leveler, more uniform shade, and is faster to washing, plumper, softer, and of more uniform feel than leather prepared by any known method.

Example VIII Nine hundred pounds of drained B outh American sheepskin skivers which have been treated inthe beamhouse for the manufacture of glove leather and which have been pickled with sulfuric acid and common salt are treated for 10 minutes at a temperature of 8011 in a revolving tanning" drum with a solution prepared by dissolving 45 pounds of common salt in 20 gallons of water.

A tanning bath is prepared by boiling together in 17 gallons of water 72 pounds of commercially prepared basic chromium sulfate (containing 23.2% of chromium calculated as CrzOa) and 36 pounds of sodium formate and allowing the reof sodium bicarbonate (NaI-lCOi) in 10 gallons of water at F. This solution is added, in one addition through the hollow trunnion, to the revolving drum containing the partiallytanned sheepskin skivers. The partially-tanned sheepskin skivers areallowed to drum in the sodium bicarbonate solution at a temperature of 80 F. for 30 minutes.

The solid door of the tanning drum is replaced by a perforated door. The drum is allowed to revolve. Water at a temperature of 80, F. is allowed to flow through the revolving drum containing the partially-tanned sheepskin skivers for 20 minutes. Excess water is drained from the drum and the perforated door is replaced by a solid door.

A solution is prepared by dissolving 8 pounds of sodium bicarbonate in 10 gallons of water at utes at a temperature of 80 F.

The solid door of the tanning drum is replaced by a perforated door. The drum is allowed to perature of Ithe rinsing water is raised to n revolve. Water at a temperature of 80 F, 3,}.

The sheepskin asoaerr lowed to flow through the revolving drum consoft, level tan color that is unusually fast to taining the partially tanned sheepskin skivers washin g. for 10 minutes. Excess water is allowed to drain Crusted glove leather prepared from pickled from the drum. The perforated door of the drum sheepskin skivers by the above method has is replaced by a solid door. markedly higher tensile strength, smoother- A solution is prepared by boiling 9 pounds of grain and plumper feel than corresponding the synthetic dyestufI-Pontachrome Brown G leather prepared by prior art methods. (C. I. No. 238) in 50 gallons of water. The dye- The invention is' not limited to the process of stuff solution is allowed to cool to a temperature preparing leather from pickled sheepskins. It of 100 F. Three pounds of fustic tanningv ex- 10 may be applied to other pickled skins. For extract are added to the synthetic dyestuff soluample, it may be applied to cowhides, horsetion. The resulting solution constitutes thedyehides, deerskins, pigskins, peccary skins, goatbath. The dyebath is added, in one addition skins, calfskins, cabretta skins and other skins through the hollow trunnion, to the revolying suitable for the manufacture of chrome-tanned drum containing the partially-tanned sheepskin 5 leather. Furthermore, the present invention is skivers. The partially-tanned sheepskinskiversnot limited to the manufacture of chrome-tanned are drummed in the dyebath for 30 at grain garment leather. It may be used for mana temperature of 100 F. ufacturing other types of chrome-tanned leather. A solution is prepared by dissolving 12 pounds For example, it may be used for manufacturing of muriatic acid (approximately 32% hydrochloo sueded glove leather, 'sueded garment leather, ric acid) in 10 gallons of water at 100 F. This sueded shoe leather, grain glove leather, grain solution is slowly added through the hollow trunshoe leather, and other types of chrome-tanned nion to the revolving drum containing the dyed leather. Further types of leather which may be partially tanned sheepskin skivers. The drummanufactured by the present invention will be ming is continued for minutes. The solid door apparent. of the drum is replaced by a perforated d As many apparently widelyeditferent embodi- The drum is revolved until the excess liquor ments of this inv n io m be m wi drained from the drum. The perforated doo" departing from the spirit and scope thereof, it replaced byasolid door. is to be understood that I do not limit myself A tanning bath is prepared by boiling togth to the specific embodiments thereof except as in 8 gallons of water, 36 pounds of commercially defined in the appended claims. prepared basic chromium sulfate (containing I claim: 23.2% of chromium calculated as CrzOa) and '18, l. The process which comprises subjecting a pounds of sodium formate and allowing the pickled skin having a pH value of about 2.0 at a sulting solution to stand several hours b'efor temperature of about 80 F. for about ten minadding 40 gallons of water. This tanning'bathis I utes to the action of a salt solution; tanning it added, in one addition through the holloilv,trunk-.. v in, a chrome bath containin b i hromium nion, to the revolving drum containing the-dyed; sulfate and sodium -formate at about 80 F. for partially tanned sheepskin'skivers. The about ninety minutes; treating the skin with ming is continued for 60 minutes at a tempera -40 sodium bicarbonate solution at about 80 F. for ture of 80 F. about thirty minutes; dyeing the skin with an A solution is prepared by dissolving 5 pounds acid dye; tanning with a vegetable tanning exof sodium bicarbonate in 10 gallons of water at tract; acidifying; completing the tanning with a temperature of 80 F. This solution is added, a chrome tan bath containing basic chromium in one addition through the hollow trunnion, to sulfate and sodium formate at about 80 F. for the revolving drum containing the dyed, comaboutan hour; neutralizing with sodium bicarpletely tanned sheepskin skivers. The drum bonate; and fatliquoring. I ming is continued for 30 minutes at a tempera 2. The process-which comprises subjecting a ture of 80 F. cpickled skin havin'gpa pH value of about 2.0 to The solid door of the drum is replaced by a the action of a salt-solution; tanning it incom perforated door. Water at 100 F. is allowed pletely in a chrome tan bath containing sodium now through the revolving drum containing the formate; neutralizing; dyeing the skin with an dyed, tanned sheepskin skivers for 30 minutes. aciddye; acidifyingy completing the chrome The t mp ur of th sing water is s d tamiing. with a tan bath containing sodium for-.

t 140 F.,' and the rinse is continued for 10" minutes. An emulsion is preparedby stirring into galmate; neutralizing; and fatliquoring.

, 3'."The process which comprises tanning a H I fpickled skin having a pH value of about 2.0 inlons of wa er t ja' mli rature of 140 F., 30 completely in a chrome tan bath containing pounds of .a partially'g-sulfonated cod oil (com: sodium jformate; dyeing the skin with an acid prisin appronma e %iis cod aye-:1 completing the chrome tanning with a tan 15% unsilli n d d01i 4 jQ-207t water). This jbathfcontaining -sodium formate; and fatliqemulsion constitutes-the? fatliquor. The fat- ,uoring'. liquor is added, in one addition through the hO1 4 -7113; process which comprises tanning a low trunnion, to th r volvin m n n g pickled skin incompletely in a chrome tanning the rinsed, dyed, fully-tanned sheepskin skivers. bath-[containing a masking agent, dyeing the The drumming is continued for 30 minutes'at a skin with an acid dye, completing the tanning temperature of140" F. The fatliqilor, muyvwith{sush -c ne tanning bath containing a masktanned, dyed sheepskin skivers are removed from agent, and fatliquoring. the drum and horsed-up to drain. 5. {l'hepm ess of preparing a colored tanned The drained,,fatliquored, -fully-tanned, dyedanther which comprises tanning the material heepskin skivers are" crusted-out (dried) at a' 'I',i nc0mp1etely in a chrome tanning bath containtemperature not exceeding 120F. 3 i s a masking a ent. dyein with n acid dye.

The crusted, dyed, tanned;sheepskin skivers, and completing the tanning. prepared according to the above process may be 6, The P s 0! P eparing a colored tanned used as glove leatherflt is characterized by a leather which comprises tanning the material pickled skin having -a pH of about 2.0 to the action oi a salt solution, tanning it in a chrome bath containing basic chromium sulfate and sodium formate, treating the skin with sodium bicarbonate solutio dyeing the skin with an acid dye, tanning it with a vegetable tanning extract, acidifying it, completing the tanning with a chrome tan bath containing basic chromium sulfate and sodium formate, neutralizing it, and iatliquoring it.

8.'The process which comprises partially tanning a skin with a solution comprising a chromium salt which exhibits tanning properties and an organic acid salt selected from the group consisting of sodium formats, sodium acetate, sodium lactate, sodium oxalate, sodium glycolate and sodium adipate, dyeing the skin with a dye selected from the group consisting of acid and direct dyes, and completing the tanning with a solution comprising a chromium salt which exhibits tanning properties and an organic acid salt from the group consisting of sodium fox-mate, sodium acetate, sodium lactate, sodium oxalate, sodium glycolate and sodium adipate.

DONALD T. KIRBY.

. C'ERT-IFICATE OF CORRECTION. Patent No. 2,503,1L77- December 1; 1914.2 DONALD TAYLOR KIRB It is herebycertified that error ap pears in the printed specifiqation of theabove numbered patent requiring corretion as follows Page jjfirst column, line 51;, for "retairzing" read --rets1'ining--; page 5, first colmnn,

line 67, for 'flatliquor" read --fatliquor---; ,and second column, line 70; .for "(212205! reed "012 9 page .8, first column,'li1ie he, roi- "8Q% F." read --80 F.--; and that the said Letters Patent should be read with this correctioh therein that the same may conform to the reeord of the case in the Patent office.

Signed. and sealed this 2nd day' of February, A. D. 1915 Henry Van Arsdale, I (8091) Acting Commissioner of Patents.