US2182140A - Process for producing reserves under dyeings of ester salts of leuco vat dyestuffs - Google Patents
Process for producing reserves under dyeings of ester salts of leuco vat dyestuffs Download PDFInfo
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- US2182140A US2182140A US12106A US1210635A US2182140A US 2182140 A US2182140 A US 2182140A US 12106 A US12106 A US 12106A US 1210635 A US1210635 A US 1210635A US 2182140 A US2182140 A US 2182140A
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- dyeings
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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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S534/00—Organic compounds -- part of the class 532-570 series
- Y10S534/01—Mixtures of azo compounds
Definitions
- the sul huric acid esters of leuco vat-dyestuffs regenerate by means of acid oxidation the original vat-dyestuff (for 5 instance on the fibre) and allow to produce by this way dyeings and prints which, on account of their perfect levelness and penetration as well as good fastness properties, find a great success amongst dyers and printers.
- ester salts also allow the fabrication of fancy figured dyeings, a result which could scarcely be obtained by hitherto usual means.
- ester salts which according to this process can only be reserved with difficulty and which are not suitable for this purpose. This'drawback' may have two reasons: Certain ester salts have such a pronounced at.- finity to the cotton fibre that it is no more possible either by washing at the boil or by soaping to remove the unoxidized ester salt oil the fibre. Some ester salts are easily oxidizable respectively very sensitive to acid. The alkali and the reducing agent of the reserve paste are not suflicient to protect the ester salt against saponiflcation and oxidation. It is a fact that in many cases, not in all, these two drawbacks, which prevent the production of good reserve efiects are particular to the same ester salt. This is increasing the difliculties.
- Green dyeings made of the ester salt of the leuco dimethoxy-dibenzanthrone can, for instance, not be reserved; the aflinity thereof to the fibre is so great that this ester salt remains 5:51 on the latter as a red body.
- the discharging of working methods, by treating such a dyeing is also not practicable for the same reason.
- Some dyeings obtained from the leuco dibromodibenzpyrenequinone respectively from the leuco di-benzpyrenequinone are also for the reason of their afiinity only reserveableor dischargeable in light shades.
- the methyl-sulphuric salt of trimethylphenyl-ammonium hydroxide, the dimethylphenylbenzyl-ammonium 2 chloride, the benzylpyridinium chloride, the methylpyridinium chloride respectively the corresponding free bases and others are suitable for the present purpose.
- the insolubility of these bodies prevents them from penetrating into the fibre. Their oxidation to the dyestuif takes place outside the textile material, so that by a soaping at the boil they can be removed, whereby pure white reserves are resulting.
- the production of a pure white is also improved by a treatment in an acid bath. It is therefore recommended, when applying for instance the steam process, in'which the development is carried outby steaming, to pass the material for a short time in an acid bath after the development.
- the treatment for developing the shade by means of an acid bath is already fulfilled.
- the sodium carbonate con- 5 tained in the reserve paste is decomposed on the fibre by the acid of the bath and gaseous -car-. bonic acid is formed. This latter removes the insoluble compound of the ester salts and the quaternary ammonium off the fibre and facili- 5o tates in this way the reserving.
- the material is then dried, passed for about 3-5 seconds in a bath at 60 C. containing 36 gr. of concentrated sulphuric acid per liter, washed, soaped at the boil, rinsed and againdried.
- ester salt of the leuco-dimethoxydibenzanthrone by the ester salt of leuco-dibenzpyrene-quinone or leuco-dibromo-' dibenzpyrene-quinone as well as-bythe ester salt of the tetrahydrodianthraquinoneazine. There are accordingly obtained White reserved effects on yellow or blue ground respectively.
- Example 2 0n white material there is printed the following reserve color:
- Ester salt of dimethoxydibenzanthrone 20% 1 paste Ethylene-thioglycol Water 500 Tragacanth thickening (60%)-.. 50 Solution of sodium chlorate (10%) Sulphocyanide of ammonia 1:1) i 60 Solution of vanadate of ammonia (1%) 10 Aqueous solution of ammonia (25%) 10 the whole being brought with water to 1 liter.
- the described process may be combined with the well known process for producing dyei gs with the aid of ice color preparations which are developable by an acid treatment. Therefore, colored reserve eifects may be produced by adding to the described reserve paste an ice color preparation.
- the fabric is printed therewith and dried and then, in well known manner, steamed under acid conditions in order to develop the ice color dyeing. .
- the subsequent padding of the so prepared material with a solution of an ester salt of a leuco vat-dyestuff, further the development of 1 the ester-salt-dyeing is principally the same as described.
- Example 5 The following reserve color is printed on white material: 5 Parts Ice color preparation containing a diazo amino compound'of metanitraniline and This is then dried and steamed as given in Example 4 for a few minutes in acid steam, and
- Example 6 The following reserve color is prepared:
- Example 4 padding bath containing:
- Example 4 Example 4 Then it is dried as given in Example 4, developed in an acid bath, rinsed and soaped. Yellow reserve effects 76 tamedand padded in a.
- Parts Ice color preparation containing the nitroiamine of diazotized meta-nitra-paratoluidine and 2-hydroxy-3-naphthoylanilide in usual commercial form 100 Ammonium salt of ricinol sulphuric acid 40 Water 194 Caustic soda lye (38 36.) 16 Gum 400 Methyl-sulphuric salt of the trimethylphenylammonium chloride Zinc oxide paste (1:1) 200 This is then printed on white material, dried aged for 4 minutes as described in Example 4 in acid conditions. Afterwards it is padded in a padding solution of the same compostion as in Example 4 and developed in an acid bath. Finishing takes place as already described.
- the step which comprises producing upon the textile material local resists against the ester salts by applying to said material locally an alkaline printing paste containing a thickening agent and a water-soluble compound of the general formula wherein R1, R2, R3 and R4 designate alkyl, aralkyl or aryl radicals having no sulpho or carboxy substituents, while X stands for the anion of a watersoluble salt.
- the step which comprises producing upon the textile material local resists against the ester salts by applying to said material locally an alkaline printing paste containing a thickening agent. and dimethyl -benzylphenyl-ammoniumchlorlde.
- the step which comprises resisting local areas of the textile material against the action of said dyestufls by applying to the fabric, prior to the coloring treatment, a resist paste comprising a water-soluble salt of a quaternary ammonium agent and an alkaline agent of the type commonly employed in printing with vat dyestuffs.
- a process for producing white reserve e1- i'ects under dyeings obtained with the aid of ester salts of leuco vat dyestuffs consisting in applying to the fabric an alkaline reserve paste containing anhydrous sodium carbonate, gum thickening and dimethyl-benzyl-phenyl-ammo- 'niumchloride, drying, further padding with a socompound, a thickening anthrone and finally developing the dyeing by acid oxidation.
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Description
Patented Dec. 5, 1939 UNITED STAT-ES.
PATENT OFFICE 2,182,140 moon'ss ron rnonvcmo ansanvns UN- DER- DYEINGS OF E VAT DYESTUFFS STEB SALTS OF LEUC O Ernst Tschan, Basel, Switzerland, assignor to the firm Durand & Huguenin A. G., Basel, Switzerland 4 Claims.
The sul huric acid esters of leuco vat-dyestuffs, respectively their salts (ester salts), see United States Patent No. 1,448,251, regenerate by means of acid oxidation the original vat-dyestuff (for 5 instance on the fibre) and allow to produce by this way dyeings and prints which, on account of their perfect levelness and penetration as well as good fastness properties, find a great success amongst dyers and printers.
These ester salts also allow the fabrication of fancy figured dyeings, a result which could scarcely be obtained by hitherto usual means.
It is therefore possible to produce, for instance on a ground dyed with an ester salt, white and colored reserves. Similar methods are described in the United States Patent 1,575,958. This process consists in printing either on the white material or on a fabric padded in a bath containing a solution of an ester salt and afterwards 20 dried, a reserve paste containing either a body of alkaline reaction or a reducing agent, or both together. On the printed places the development by acid oxidation of the ester salt dyeings does not take place as the action of acid and oxidizing agent is rendered impossible. In this manner white reserves on'a colored ground can be obtained. By adding vat-dyestuffs to the reserve paste colored reserves may also be obtained.
There are, however, ester salts which according to this process can only be reserved with difficulty and which are not suitable for this purpose. This'drawback' may have two reasons: Certain ester salts have such a pronounced at.- finity to the cotton fibre that it is no more possible either by washing at the boil or by soaping to remove the unoxidized ester salt oil the fibre. Some ester salts are easily oxidizable respectively very sensitive to acid. The alkali and the reducing agent of the reserve paste are not suflicient to protect the ester salt against saponiflcation and oxidation. It is a fact that in many cases, not in all, these two drawbacks, which prevent the production of good reserve efiects are particular to the same ester salt. This is increasing the difliculties.
Amongst the hardly reserveable ester salts, some give dyeings and prints of especially good fastness and can therefore not be replaced by other ester salts.
Green dyeings made of the ester salt of the leuco dimethoxy-dibenzanthrone can, for instance, not be reserved; the aflinity thereof to the fibre is so great that this ester salt remains 5:51 on the latter as a red body. The discharging of working methods, by treating such a dyeing is also not practicable for the same reason. I
Some dyeings obtained from the leuco dibromodibenzpyrenequinone respectively from the leuco di-benzpyrenequinone are also for the reason of their afiinity only reserveableor dischargeable in light shades.
It has now been found that according to the process of this invention it is possible to produce good reserves under ester-salt dyeings, also unm der dyeings of such ester salts which could not .be reserved in satisfactory manner by the hitherto employed processes. According to this invention, on the white material, before padding, a reserve paste is printed containing-besides an alkali, especially an alkaline carbonate-a quaternary ammonium compound, i. e., a compound in which four valences of the nitrogen atom are substituted by organic radicals. One pads afterwards as usual in a solution of an estersalt, dries and develops the shade, according to the known with an oxidizing agent in the presence of acid. The methyl-sulphuric salt of trimethylphenyl-ammonium hydroxide, the dimethylphenylbenzyl-ammonium 2 chloride, the benzylpyridinium chloride, the methylpyridinium chloride respectively the corresponding free bases and others are suitable for the present purpose. The insolubility of these bodies prevents them from penetrating into the fibre. Their oxidation to the dyestuif takes place outside the textile material, so that by a soaping at the boil they can be removed, whereby pure white reserves are resulting.
The production of a pure white is also improved by a treatment in an acid bath. It is therefore recommended, when applying for instance the steam process, in'which the development is carried outby steaming, to pass the material for a short time in an acid bath after the development. When applying the other processes (nitrite-bichromate-chromate), the treatment for developing the shade by means of an acid bath is already fulfilled. .The sodium carbonate con- 5 tained in the reserve paste is decomposed on the fibre by the acid of the bath and gaseous -car-. bonic acid is formed. This latter removes the insoluble compound of the ester salts and the quaternary ammonium off the fibre and facili- 5o tates in this way the reserving.
This new process allows the production of a new interesting style, which could not hitherto be executed. This special style is only obtainable with ester salts of leuco vat-dyestuffs, but it can Gr. Anhydrous sodium carbonate 150 Water 300 Gum thickening (1:1) i e 500 Benzylphenylammonium chloride 50 1000 Then the material is dried and padded in a full bath containing the following solution:
' Gr. Ester salt of leuco dimethoxydibenzanthrone 20% paste 1 80f Water I 500 Neutral tragacanth thickening 50 Solution of sodium carbonate (10%) 20 Solution of sodium nitriate (20% .L. 50
not be realized themselves.
The following examples illustrate the present invention.
by means of the vat-dyestufl's Example 1 0n white material there is printed the following reserve C0101:
the whole be ng brought with water to 1 liter.
The material is then dried, passed for about 3-5 seconds in a bath at 60 C. containing 36 gr. of concentrated sulphuric acid per liter, washed, soaped at the boil, rinsed and againdried.
By this way white reserves on green ground are obtained. I
It is possible to replace the ester salt of the leuco-dimethoxydibenzanthrone by the ester salt of leuco-dibenzpyrene-quinone or leuco-dibromo-' dibenzpyrene-quinone as well as-bythe ester salt of the tetrahydrodianthraquinoneazine. There are accordingly obtained White reserved effects on yellow or blue ground respectively.
Example 2 0n white material there is printed the following reserve color:
the whole being brought with water to 1 liter.
Thisis then dried and developed as given in Example 1. Pure white effects on oliveground are obtained.-
' Example 3 on white material there is printed a reserve color made of:
Sodium carbonate 150 Water 270 Gum thickening (1:1') 500 -Benzylpyridinium chloride v phuric acid per liter, at
' Gra arsaiso This is then dried and padded in a full bath containing the following solution: I.
Ester salt of dimethoxydibenzanthrone 20% 1 paste Ethylene-thioglycol Water 500 Tragacanth thickening (60%)-.. 50 Solution of sodium chlorate (10%) Sulphocyanide of ammonia 1:1) i 60 Solution of vanadate of ammonia (1%) 10 Aqueous solution of ammonia (25%) 10 the whole being brought with water to 1 liter.
' Thereupon, it is dried, steamed for 8 minutes, passed in the open-width for a few seconds in a bath containing 18 gr. of concentrated sul-' a temperature of 50? 0., rinsed, soaped at the boil, rinsed again and dried.
The described process may be combined with the well known process for producing dyei gs with the aid of ice color preparations which are developable by an acid treatment. Therefore, colored reserve eifects may be produced by adding to the described reserve paste an ice color preparation. The fabric is printed therewith and dried and then, in well known manner, steamed under acid conditions in order to develop the ice color dyeing. .The subsequent padding of the so prepared material with a solution of an ester salt of a leuco vat-dyestuff, further the development of 1 the ester-salt-dyeing is principally the same as described.
This modification of the process is illustrated by the following examples, the parts being by weight.
Example 4 The following reserve color is prepared:
Parts An ice color preparation containing a diazoamino compound of 4-nitro-2-aminoanisol and 2-hydroxy-B-naphthoyl-p-anisidide, in the commercial form Caustic soda lye 38 B Alcohol 'Water Gum Zinc oxide paste (1:1) Methyl-sulphuric salt of trimethylphenylammonium chloride 30 After printing this is driedand aged for 4 minutes, while spraying a mixture of acetic acid and formic acid (equal parts) into the apparatus to bring the steam to acid reaction to litmus paper. Then there is padded in the following padding bath:
Parts Ester salt of leuco-dimethoxydibenzathrone 20% paste- Water i 500 Tragacanth thickening";
Sodium carbonate 2 Sodium nitritm 15 the whole being brought to one liter.
After padding it is dried and treated for 8 minutes at 6070 C. in a bath containing 36 gr.
of concentrated sulphuric acid per liter. Then it is rinsed, neutralized with some sodium carbonate and soaped at the reserves on green ground boil. Thus bright red are obtained.
Example The following reserve color is printed on white material: 5 Parts Ice color preparation containing a diazo amino compound'of metanitraniline and This is then dried and steamed as given in Example 4 for a few minutes in acid steam, and
then padded in the following padding bath:
Parts Ester salt of leuco-dimethoxydibenzathrone 25 20% paste 50 Water 500 Tragacanth thickening 50 Solution of sodium chlorate 80 Sulphocyanide of ammonia (1:1) 40 30 Solution of vanadate of ammonia (l%) 10 Aqueous ammonia (20%) 20 the whole being brought with water to one liter. It is then dried, steamed for 8 minutes 85 and thereupon treated in a bath containing 36 gr. of concentrated sulphuric acid per liter. To finish it is soaped, neutralized with some soda and soaped at the boil.
Bright orange reserves on green 0 thus obtained.
ground are Example 6 The following reserve color is prepared:
, Parts Icev color preparation containing diamamino compound of ortho-chloraniline and di-aceto-acetic-o-tolidide in the usual commercial form 80 Caustic soda (38 Be.) 30
50 Alcohol g 30 Water 30 Gum 500 Zinc oxide paste (1:1) 00 Methyl-sulphuric salt of the trimethylphenylammonium chloride This is printed on white material, dried,
steamed as given in Example 4 padding bath containing:
Ester salt of the leuco vat-dyestufl as per Example 4 of German Specification No.
' 212,471 20% paste 60 Hot water 500 Tragacanth thickening 50 Sodium carbonate 2% 7 Sodium nitrite u I the whole being brought with water to one liter.
Then it is dried as given in Example 4, developed in an acid bath, rinsed and soaped. Yellow reserve effects 76 tamedand padded in a.
on. ol v g u d are-ob- 7 Example 7 The following reserve color is prepared:
. Parts Ice color preparation containing the nitroiamine of diazotized meta-nitra-paratoluidine and 2-hydroxy-3-naphthoylanilide in usual commercial form 100 Ammonium salt of ricinol sulphuric acid 40 Water 194 Caustic soda lye (38 36.) 16 Gum 400 Methyl-sulphuric salt of the trimethylphenylammonium chloride Zinc oxide paste (1:1) 200 This is then printed on white material, dried aged for 4 minutes as described in Example 4 in acid conditions. Afterwards it is padded in a padding solution of the same compostion as in Example 4 and developed in an acid bath. Finishing takes place as already described.
Red-reserve effects on green ground are tained,
Instead of the methyl-sulphuric salt of trlmethylphenylammonium chloride, one can use with similar result another quaternary ammonium compound, for example one of those mentioned in the introduction of this specification.
What I claim is: I
1. In the process of producing reserve effects under dyeingscbtained with the aid of ester salts of leuco vat dyestuffs, the step which comprises producing upon the textile material local resists against the ester salts by applying to said material locally an alkaline printing paste containing a thickening agent and a water-soluble compound of the general formula wherein R1, R2, R3 and R4 designate alkyl, aralkyl or aryl radicals having no sulpho or carboxy substituents, while X stands for the anion of a watersoluble salt.
2. In the process of producing reserve effects under dyeings obtained with the aid of ester salts of leuco vat dyestufls, the step which comprises producing upon the textile material local resists against the ester salts by applying to said material locally an alkaline printing paste containing a thickening agent. and dimethyl -benzylphenyl-ammoniumchlorlde.
3. In the process of producing reserve eflects under dyeings obtained with the aid of ester salts of leuco vat dyestufls, the step which comprises resisting local areas of the textile material against the action of said dyestufls by applying to the fabric, prior to the coloring treatment, a resist paste comprising a water-soluble salt of a quaternary ammonium agent and an alkaline agent of the type commonly employed in printing with vat dyestuffs.
, 4. A process for producing white reserve e1- i'ects under dyeings obtained with the aid of ester salts of leuco vat dyestuffs, consisting in applying to the fabric an alkaline reserve paste containing anhydrous sodium carbonate, gum thickening and dimethyl-benzyl-phenyl-ammo- 'niumchloride, drying, further padding with a socompound, a thickening anthrone and finally developing the dyeing by acid oxidation.
ERNST TECH-AN.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE2182140X | 1934-03-26 |
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US2182140A true US2182140A (en) | 1939-12-05 |
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US12106A Expired - Lifetime US2182140A (en) | 1934-03-26 | 1935-03-20 | Process for producing reserves under dyeings of ester salts of leuco vat dyestuffs |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3080462A (en) * | 1954-10-07 | 1963-03-05 | Gen Electric | Circuit breaker |
-
1935
- 1935-03-20 US US12106A patent/US2182140A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3080462A (en) * | 1954-10-07 | 1963-03-05 | Gen Electric | Circuit breaker |
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