US2474785A - Process for printing with sulphuric esters of leuco vat dyestuffs - Google Patents

Process for printing with sulphuric esters of leuco vat dyestuffs Download PDF

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US2474785A
US2474785A US687520A US68752046A US2474785A US 2474785 A US2474785 A US 2474785A US 687520 A US687520 A US 687520A US 68752046 A US68752046 A US 68752046A US 2474785 A US2474785 A US 2474785A
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printing
parts
leuco
acid
ester
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William B Hardy
Elizabeth M Hardy
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Wyeth Holdings LLC
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American Cyanamid Co
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/628—Compounds containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/28—Esters of vat dyestuffs

Definitions

  • This invention relates to an improved process for printing textile fibers and fabrics with diflicultly oxidizable sulfuric ester salts of leuco vat dyes using the dichromate-acid vapor developing method.
  • Some of the disadvantages of the chlorate acid vapor process are overcome by a procedure in which a milder oxidizing agent, such as a dichromate, is incorporated into the printing paste containing sulfuric esters of leuco vat dyestuffs, and aging effected with. acid vapors, such as, for example, mixed acetic acid-formic acid vapors. It is with this dichromate process that the improvement of the present invention deals.
  • a milder oxidizing agent such as a dichromate
  • the dichromate-acid vapor process while it does not attack sensitive dyes, is also subject to a number of drawbacks.
  • the principal one is that certain. sulfuric esters of leuco vat dyestuffs which are difii'cultly oxidizable .do not fully develop during the acid vapor treatment within the usual aging periods of about 1-5 minutes, even when large excesses of the oxidizing agent are used. Also, drastic increases in the aging timete. g., up to 20 minutes, do not bring aboutfull development.
  • a further drawback: is that development. of the incompletely developed color sometimes continues slowly during after-storage of the fabric which results in a change of shade. As a result of the above drawbacks the dichromate-acid vapor process has been restricted to result the dichromate-a-cid vapor process has not.
  • aniline sulfonic acid radical will be used inthe claims to cover either type" of compound, and it will be used therein in no other sense.
  • the substituent in the aniline sulfonic acid is an aliphatic hydrocarbon radical having not more than one double bond. There may be present one substituent or a plurality.
  • the sulfonic acids which may be considered as development accelerators or catalysts may be added either to the printing paste or tothe dry ester salts used in preparing aprinting formula. When properly used, fast prints are obtained of excellent strength and brilliance, the dyeing strength being increased inmany cases from values as low as 10% to substantially the full color value.
  • the position. of the sulfonic acid does not appear to be vital.
  • an oxidation accelerator or catalyst which are so marked in the substituted aniline sulfonic acids of the present invention, are quite surprising because the same general type of compound has been used in processes of printing with other and stronger oxidizing agents, such as chlorates. In such a process the compounds exert the opposite effect and prevent over-oxidation, particularly when used in a process in which development is effected by steaming and not by acid vapors. The reasons for the contrary effects in the different processes are likewise not known.
  • the process of the present invention is strictly limited to an improved dichromate-acid vapor printing process in which leuco vat dye ester salts are used which are diificultly oxidizable in this process. It should not be confused with processes in which develop ment is efiected by passing the printed goods through a liquid bath containing an oxidizing agent, such as nitrite or dichromate. In general, vat dye ester salts which are difficult to oxidize by this bath process are also difficult to oxidize by the dichromate-acid vapor process.
  • the amount of oxidation accelerator or dyeing assistant is not critical. Apparently, the compound does not take part strictly as a reactant, and a considerably smaller amount of the accelerator may be used than oxidizing agent. In general an amount of accelerator which is somewhat less than the weight of the dyestuff ester gives best results. However, good results are obtained from quite a wide range of proportions. It is, of course, necessary to add suflicient accelerator to produce rapid oxidation, the minimum amount varying with different accelerators and with difierent dyes. Small traces of accelerator are, of course, not effective, as the reaction appears not to be a purely catalytic one in which minute quantities of accelerator are capable of carrying on the reaction of very large amounts of dyestufi and oxidizer.
  • the prints are not only of excellent strength and brilliance, the strength being increased in many cases from as low as to substantially full color value, but that the process is controllable, that is to say, the rate of development can be influenced by the addition of varying amounts of accelerator.
  • prints can be made to develop in a shorter time than normal, for example, in a few minutes, or the color development may be caused to proceed more slowly so that the reaction rate can be controlled within wide limits, in accordance with the desire of the operator.
  • prints are obtained which show improved levelness and freedom from specks, and they do not show any deterioration in shade due to after development.
  • the accelorator permits operation without a larger excess of oxidizing agent.
  • Example 1 7 parts of the sodium salt of the disulfuric acid ester of leuco tetrabrornoindigo (equivalent to 4.35 parts of tetrabromoindigo) are blended with 2 parts of 2-amino, 3-5-dimethylbenzene sulfonic acid (Na salt) and 1.1 parts of sucrose to give a powder containing approximately 43% real dye.
  • A. printing paste is made from this blended powder, using the following ingredients:
  • the cloth is printed with this paste and the resulting prints are aged in formic and acetic acid vapors.
  • the prints develop to substantially full color value, in 1 to 3 minutes. If no metaxylidine sulfonic acid is present in the powder, only 10-15% of the expected color value is obtained even after as long as 10 minutes aging.
  • Example 2 7 parts of the crude sodium salt of the disulfuric ester of leuco tetrabromoindigo (equivalent to 4.35 parts of tetrabromoindigo) are blended with 2 parts of sodium 2-amino-5-methylbenzene sulfonate and 1.1 parts of sucrose to give a powder containing approximately 43% real dye. When this powder is incorporated into a printing paste as described in Example 1, printed and aged, prints of substantially full color value were obtained. In the absence of the sodium paminotoluene sulfonate only about 10% of the expected color value is obtained.
  • Example 3 6 parts of crude sodium salt of the disulfuric ester of leuco tetrabromoindigo (equivalent to 3.59 parts of tetrabromoindigo) were blended with 2 parts of sodium N,N-diethylaniline 4- sulfonate and 0.28 part of sucrose to give a powder of approximately 43% dye content.
  • i odi-nn diethylaniline sulfonate also greatly increases the printing strength of the blended powder of the sodium salt of the disulfuric ester of leuco 7,7-dimethyl 5,5 dichlorothioindigo over that of a similar powder containing no sodium diethylaniline sulfonate.
  • Example 4 ample 1, gives prints of essentially full strength on short aging. The required. color value is. not obtained under identical conditions in the absence of sodium diallylaniline sulfonate.
  • Example 5 7 parts of the sodium salt of the disulfuric acid ester of leuco 7,7-dimethyl-5,5-dichlorothioindigo (containing 3.9 parts of 7,7'-dimethyl- 5,5'-dichlorothioindigo) are blended with 1.66 parts of 2-amino 3,5-dimethylbenzene sulfonic acid sodium salt to give a powder of approximately 44% real dye content. Prints obtained from this powder by the procedure described in Example 1 develop to substantially full color value on 1 to 3 minutes aging. In the absence of the meta-xylidine sulfonic acid sodium salt, only to 20% of the expected color value is obtained after 10 minutes aging.
  • meta-xylidine sulfonic acid sodium salt in the above example is replaced by the sodium salt of N-benzyl sulfanilic acid only about 20% of the expected color value is obtained after 10 minutes aging.
  • Example 6 9 parts of the sodium salt of the disulfuric acid ester of leuco 4,5,4',5-dibenzthioindigo (containing 4.67 parts of real 4,5,4,5-dibenzthioindigo) are blended with 1.38 parts 2-amino 3,5-dimethylbenzene sulfonic acid sodium salt to give a powder containing approximately 45% real dye. Prints of substantially full color value are obtained from this powder by means of the previously described printing formula and in an aging time of 1 to 3 minutes. If no meta-xylidine sulfonic acid sodium salt is included in the powder, only 10 to 20% of the expected color value is obtained even after a 10 minute aging.
  • the leuco vat dye ester salt used in this example constitutes one of the few exceptions referred to in the introductory portion of the specification.
  • This ester salt has been characterized in the literature as being fairly readily oxidizable in liquid development processes where the leuco ester salt is used primarily for dyeing rather than printing. In the dichromate-acid vapor process of developing prints this leuco ester salt is to be characterized as difficultly oxidizable since it will not develop to full color value in a reasonable time without the use of the accelerators of the present invention.
  • Example 7 4.7 parts of the sodium salt of the disulfuric ester of leuco 4,4-dimethyl-6,6-dichlorothioindigo (containing 2.55 parts of real dye) are blended with 1.05 parts of Z-amino 3,5-dimethylbenzene sulfonic acid sodium salt and 1.54 parts of sucrose to give a powder containing 36% real dye.
  • Prints obtained from this product by the procedure described in Example 1 give essentially the full color value on aging for 1 to 3 minutes. In the absence of the meta-xylidine sulfonic acid, only a 5% to 10% of the expected color value is obtained even after 10 minutes aging.
  • a process for printing difficultly oxidizable sulfuric ester salts of leuco vat dyestuffs of the indigoid type which comprises printing the ester salts with dichromates and in the presence of an efiective amount of an aniline sulfonic acid radical, substituted by at least one aliphatic hydrocarbon radical containing not more than one double bond, and developing the print with acid vapors.
  • a process according to claim 1 in which the substituted aniline sulfonic acid is N,N-diethylaniline-para-sulfonic acid.
  • a process according to claim 1 in which the sulfuric ester salt is the disulfuric ester salt of leuco 4,5,4',5'-dibenzthioindigo.

Description

Patented June 28, 1949 PROCESS FOR PRINTING: WITH SULPHURIG ESTERS F LEUCO VAT DYESTUFFS William B. Hardy and Elizabeth M. Hardy, Bound Brook, N. J., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application July 31,1946, Serial N0. 687,520
7 Claims.
This invention relates to an improved process for printing textile fibers and fabrics with diflicultly oxidizable sulfuric ester salts of leuco vat dyes using the dichromate-acid vapor developing method.
Printing of textiles with sulfuric ester salts of leuco vat dyes has been carried out by two general procedures. One of the processes incorporates a powerful oxidizing agent in the printing paste, such as a chlorate, and the print is developed by treatment with steam and. acid vapors. This process is generally usable with all stable dyestuffs. However, it is open to a very serious disadvantage when the dye mixture printed contains dyes which are sensitive to oxidizing agents. In the process such colors are rather severely attacked and the use of processes involvingstrong oxidizing agents such as chlorates have, therefore, been definitely limited in their field of utility.
Some of the disadvantages of the chlorate acid vapor process are overcome by a procedure in which a milder oxidizing agent, such as a dichromate, is incorporated into the printing paste containing sulfuric esters of leuco vat dyestuffs, and aging effected with. acid vapors, such as, for example, mixed acetic acid-formic acid vapors. It is with this dichromate process that the improvement of the present invention deals.
The dichromate-acid vapor process, while it does not attack sensitive dyes, is also subject to a number of drawbacks. The principal one is that certain. sulfuric esters of leuco vat dyestuffs which are difii'cultly oxidizable .do not fully develop during the acid vapor treatment within the usual aging periods of about 1-5 minutes, even when large excesses of the oxidizing agent are used. Also, drastic increases in the aging timete. g., up to 20 minutes, do not bring aboutfull development. A further drawback: is that development. of the incompletely developed color sometimes continues slowly during after-storage of the fabric which results in a change of shade. As a result of the above drawbacks the dichromate-acid vapor process has been restricted to result the dichromate-a-cid vapor process has not.
been usable with a certain class of sulfuric estersof leuco vat dyes, including. some of the import:- ant vat colors.
According to the: present inventionit. has been,
' able sulfuric esters of leuco vat dyestuffs.
found that full deveIopmen-t in a short time is obtained by the dibh-romate-acid vapor process regardless of whether this radical is attached to hydrogen to form'- the free acid or toa basic radical to form a salt, the term aniline sulfonic acid radical" will be used inthe claims to cover either type" of compound, and it will be used therein in no other sense.
The substituent in the aniline sulfonic acid is an aliphatic hydrocarbon radical having not more than one double bond. There may be present one substituent or a plurality. The sulfonic acids which may be considered as development accelerators or catalysts may be added either to the printing paste or tothe dry ester salts used in preparing aprinting formula. When properly used, fast prints are obtained of excellent strength and brilliance, the dyeing strength being increased inmany cases from values as low as 10% to substantially the full color value.
Improved results of the present invention are obtained regardless of whether the alkyl or alkenyl group orgroups are attached to a carbon atom of the benzene ring or to the nitrogen atom. This is unusual because ordinarily the presence of an alkyl'or alkenyl group produces chemical compounds of quite different characteristics, dependingon whether it is a ring substituent or is attached. to the nitrogen. It is not known why the contrary is the case in the process and compositions of the present invention, and it is not desiredto limit the same to any theory. Among the typical compounds included in the present invention are sulfonic acids of toluidines, xylidines, cumid'ines, cymi'dines and N-mono and dialkyl or alkenyl anilines, such as diethylaniline,. diallylaniline, and the like. The position. of the sulfonic acid does not appear to be vital.
. There is some variation in degree of positive results obtained with individual members of the substituted aniline sulfonic acids of the present invention, but the. class as a whole gives useful improvements in printing with difficultly oxidiz- It is an advantageof the present invention that the added compounds do not themselves form disturbing. oxidationcolors under the conditions of operation.
The improved results which are obtainable with the printing assistants of the present invention appear to be quite specific to the class. Normally, the chemical behavior of alkyl substituted compounds and aralkyl substituted compounds is quite similar. In the present case this does not hold true and sulfonic acids of N-lbenzyl anilines do not show the great improvement which is typical of the compounds of the present invention. The underlying chemical reason for this sharp difference is not as yet proven, and no theory is advanced why such closely related aralkyl derivatives do not possess the valuable properties of the assistants of the present invention.
The properties of an oxidation accelerator or catalyst, which are so marked in the substituted aniline sulfonic acids of the present invention, are quite surprising because the same general type of compound has been used in processes of printing with other and stronger oxidizing agents, such as chlorates. In such a process the compounds exert the opposite effect and prevent over-oxidation, particularly when used in a process in which development is effected by steaming and not by acid vapors. The reasons for the contrary effects in the different processes are likewise not known.
It should be emphasized that the process of the present invention is strictly limited to an improved dichromate-acid vapor printing process in which leuco vat dye ester salts are used which are diificultly oxidizable in this process. It should not be confused with processes in which develop ment is efiected by passing the printed goods through a liquid bath containing an oxidizing agent, such as nitrite or dichromate. In general, vat dye ester salts which are difficult to oxidize by this bath process are also difficult to oxidize by the dichromate-acid vapor process.
There are, however, a few exceptions where a leuco vat dye ester salt is fairly readily oxidized by the bath process and is difiiculty oxidizable by the dichromate-acid vapor process, requiring one of our catalysts for full development.
It is an advantage of the present invention that the amount of oxidation accelerator or dyeing assistant is not critical. Apparently, the compound does not take part strictly as a reactant, and a considerably smaller amount of the accelerator may be used than oxidizing agent. In general an amount of accelerator which is somewhat less than the weight of the dyestuff ester gives best results. However, good results are obtained from quite a wide range of proportions. It is, of course, necessary to add suflicient accelerator to produce rapid oxidation, the minimum amount varying with different accelerators and with difierent dyes. Small traces of accelerator are, of course, not effective, as the reaction appears not to be a purely catalytic one in which minute quantities of accelerator are capable of carrying on the reaction of very large amounts of dyestufi and oxidizer.
It is an advantage of the present invention that the prints are not only of excellent strength and brilliance, the strength being increased in many cases from as low as to substantially full color value, but that the process is controllable, that is to say, the rate of development can be influenced by the addition of varying amounts of accelerator. Thus, prints can be made to develop in a shorter time than normal, for example, in a few minutes, or the color development may be caused to proceed more slowly so that the reaction rate can be controlled within wide limits, in accordance with the desire of the operator. In every case prints are obtained which show improved levelness and freedom from specks, and they do not show any deterioration in shade due to after development. It is a further advantage of the invention that the accelorator permits operation without a larger excess of oxidizing agent.
The invention will be described in greater de tail in conjunction with the following examples, which are typical. The parts are by weight.
Example 1 7 parts of the sodium salt of the disulfuric acid ester of leuco tetrabrornoindigo (equivalent to 4.35 parts of tetrabromoindigo) are blended with 2 parts of 2-amino, 3-5-dimethylbenzene sulfonic acid (Na salt) and 1.1 parts of sucrose to give a powder containing approximately 43% real dye.
A. printing paste is made from this blended powder, using the following ingredients:
Parts Color 3 Urea 6 A mixture of 4 parts acetamide, 4 parts diethylene glycol and 2 parts furfuryl alcohol 3 Water 11 A 15% gum paste in water Ammonium chloride .75 25% ammonia 2.0 Sodium dichromate 5.0
The cloth is printed with this paste and the resulting prints are aged in formic and acetic acid vapors. The prints develop to substantially full color value, in 1 to 3 minutes. If no metaxylidine sulfonic acid is present in the powder, only 10-15% of the expected color value is obtained even after as long as 10 minutes aging.
Example 2 7 parts of the crude sodium salt of the disulfuric ester of leuco tetrabromoindigo (equivalent to 4.35 parts of tetrabromoindigo) are blended with 2 parts of sodium 2-amino-5-methylbenzene sulfonate and 1.1 parts of sucrose to give a powder containing approximately 43% real dye. When this powder is incorporated into a printing paste as described in Example 1, printed and aged, prints of substantially full color value were obtained. In the absence of the sodium paminotoluene sulfonate only about 10% of the expected color value is obtained.
Example 3 6 parts of crude sodium salt of the disulfuric ester of leuco tetrabromoindigo (equivalent to 3.59 parts of tetrabromoindigo) were blended with 2 parts of sodium N,N-diethylaniline 4- sulfonate and 0.28 part of sucrose to give a powder of approximately 43% dye content. Prints obtained from this product by the usual procedure of printing and dyeing described in Example 1, develop to full color value on short aging. Only a small fraction (about 10%) of the desired color value can be obtained in the absence of sodium diethylaniline sulfonate.
i odi-nn diethylaniline sulfonate also greatly increases the printing strength of the blended powder of the sodium salt of the disulfuric ester of leuco 7,7-dimethyl 5,5 dichlorothioindigo over that of a similar powder containing no sodium diethylaniline sulfonate.
Example 4 ample 1, gives prints of essentially full strength on short aging. The required. color value is. not obtained under identical conditions in the absence of sodium diallylaniline sulfonate.
Example 5 7 parts of the sodium salt of the disulfuric acid ester of leuco 7,7-dimethyl-5,5-dichlorothioindigo (containing 3.9 parts of 7,7'-dimethyl- 5,5'-dichlorothioindigo) are blended with 1.66 parts of 2-amino 3,5-dimethylbenzene sulfonic acid sodium salt to give a powder of approximately 44% real dye content. Prints obtained from this powder by the procedure described in Example 1 develop to substantially full color value on 1 to 3 minutes aging. In the absence of the meta-xylidine sulfonic acid sodium salt, only to 20% of the expected color value is obtained after 10 minutes aging.
If the meta-xylidine sulfonic acid sodium salt in the above example is replaced by the sodium salt of N-benzyl sulfanilic acid only about 20% of the expected color value is obtained after 10 minutes aging.
Example 6 9 parts of the sodium salt of the disulfuric acid ester of leuco 4,5,4',5-dibenzthioindigo (containing 4.67 parts of real 4,5,4,5-dibenzthioindigo) are blended with 1.38 parts 2-amino 3,5-dimethylbenzene sulfonic acid sodium salt to give a powder containing approximately 45% real dye. Prints of substantially full color value are obtained from this powder by means of the previously described printing formula and in an aging time of 1 to 3 minutes. If no meta-xylidine sulfonic acid sodium salt is included in the powder, only 10 to 20% of the expected color value is obtained even after a 10 minute aging.
The leuco vat dye ester salt used in this example constitutes one of the few exceptions referred to in the introductory portion of the specification. This ester salt has been characterized in the literature as being fairly readily oxidizable in liquid development processes where the leuco ester salt is used primarily for dyeing rather than printing. In the dichromate-acid vapor process of developing prints this leuco ester salt is to be characterized as difficultly oxidizable since it will not develop to full color value in a reasonable time without the use of the accelerators of the present invention.
Example 7 4.7 parts of the sodium salt of the disulfuric ester of leuco 4,4-dimethyl-6,6-dichlorothioindigo (containing 2.55 parts of real dye) are blended with 1.05 parts of Z-amino 3,5-dimethylbenzene sulfonic acid sodium salt and 1.54 parts of sucrose to give a powder containing 36% real dye. Prints obtained from this product by the procedure described in Example 1 give essentially the full color value on aging for 1 to 3 minutes. In the absence of the meta-xylidine sulfonic acid, only a 5% to 10% of the expected color value is obtained even after 10 minutes aging.
We claim:
1. A process for printing difficultly oxidizable sulfuric ester salts of leuco vat dyestuffs of the indigoid type which comprises printing the ester salts with dichromates and in the presence of an efiective amount of an aniline sulfonic acid radical, substituted by at least one aliphatic hydrocarbon radical containing not more than one double bond, and developing the print with acid vapors.
2. A process according to claim 1 in which the substituted aniline sulfonic acid is 2-amino-3,5- dimethylbenzene sulfonic acid.
3. A process according to claim 1 in which the substituted aniline sulfonic acid is N,N-diethylaniline-para-sulfonic acid.
4. A process according to claim. 1 in which the substituted aniline sulfonic acid is a paratoluidine sulfonic acid. V
5. A process according to claim 1 in which the sulfuric ester salt is the disulfuric ester salt of leuco tetrabromoindigo.
6. A process according to claim 1 in which the sulfuric ester salt is the disulfuric ester salt of a dimethyl-dichlorothioindigo.
'7. A process according to claim 1 in which the sulfuric ester salt is the disulfuric ester salt of leuco 4,5,4',5'-dibenzthioindigo.
WILLIAM B. HARDY. ELIZABETH M. HARDY.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,779,305 Brandt Oct. 21, 1930! 2,234,301 Niederhausern Mar. 11, 1941 FOREIGN PATENTS Number Country Date 398,571 France Mar. 26, 1909
US687520A 1946-07-31 1946-07-31 Process for printing with sulphuric esters of leuco vat dyestuffs Expired - Lifetime US2474785A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR398571A (en) * 1908-05-30 1909-06-08 Farbenfab Vorm Bayer F & Co Printing process
US1779305A (en) * 1928-12-22 1930-10-21 Firm Durand & Huguenin S A Process for obtaining fast dyeings and prints with vat dyestuffs
US2234301A (en) * 1937-03-01 1941-03-11 Firm Durand & Huguenin S A Production of fast dyeings and printings by means of ester salts of leuco vat-dyestuffs

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR398571A (en) * 1908-05-30 1909-06-08 Farbenfab Vorm Bayer F & Co Printing process
US1779305A (en) * 1928-12-22 1930-10-21 Firm Durand & Huguenin S A Process for obtaining fast dyeings and prints with vat dyestuffs
US2234301A (en) * 1937-03-01 1941-03-11 Firm Durand & Huguenin S A Production of fast dyeings and printings by means of ester salts of leuco vat-dyestuffs

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