US3442601A - Process for printing textile materials of natural or regenerated cellulose with reactive dyestuffs - Google Patents
Process for printing textile materials of natural or regenerated cellulose with reactive dyestuffs Download PDFInfo
- Publication number
- US3442601A US3442601A US541129A US3442601DA US3442601A US 3442601 A US3442601 A US 3442601A US 541129 A US541129 A US 541129A US 3442601D A US3442601D A US 3442601DA US 3442601 A US3442601 A US 3442601A
- Authority
- US
- United States
- Prior art keywords
- parts
- fabric
- water
- sodium
- printed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
- C09B62/006—Azodyes
-
- 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
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/918—Cellulose textile
Definitions
- the present invention provides a process for printing textile materials of natural or regenerated cellulose by means of reactive dyestuffs.
- the reactive dyestuff is fixed fast on textile material of natural or regenerated cellulose by applying the dyestuff to the textile material in the first phase by means of a printing paste which contains water and a thickening agent and-after drying-padding the print in the second phase with an aqueous liquor which contains an agent having an alkaline reaction, steaming the material for to 30 seconds at about 110 to 115 C. and subsequently rinsing and soaping it, rinsing it again and finally drying it.
- reactive dyestuffs can be fixed fast on textile materials of natural or regenerated cellulose, without using the steaming process, by printing the reactive dyestuff on the textile material in the first phase by means of a printing paste which contains water and a thickening agent and-after dryingpadding the print in the second phase with an aqueous liquor which contains an agent having an alkaline reaction and exposing it subsequently to an air passage.
- the fixing process according to the present invention possesses several advantages. Since the steaming process is no longer necessary, a considerable amount of energy is saved per meter of printed material.
- the present invention possesses the advantage that the equilibrium reactive dyestuff+cellulose:reactive dyestuff-cellulose is shifted considerably in favour of the dyed cellulose.
- a reduction of the tinctorial strength can be 3,442,601 Patented May 6, 1969 avoided, particularly when dyestuffs are used which are easily resaponified at the binding dyestuff-fibre on steaming under the influence of alkalies.
- the reducing influence of the cellulose occurring at the steaming temperature provokes changes of the tints not only when individual dyestuffs are used but also when dyestuff combinations for obtaining combination shades are applied.
- organic dyestuffs there can be used according to the process of the present invention different organic dyestuff classes, for example, azo dyestuffs and anthraquinone dyestuffs which contain at least one of the known reactive groups such as for example, B-hydroxyethylsulfone.sulfuric acid ester groups, vinylsulfone groups, dichlorotriazine groups, ethionylamino groups, N-alkyl-ethionylamino groups, 2,2,3,3-tetrafluorocyclobutane-l-carbonylamino groups, 2-fluoro-2-chloro-3,3-difluorocyclobutanel-carbonylamino groups, 2,2,3,B-tetrafluorocyclobutane-1- acryloylamino groups, vinylsulfonylamino groups or 2,3- dichloroquinoxaline radicals.
- reactive groups such as for example, B-hydroxyethylsulf
- alkali metal hydroxides are preferably used as agents having an alkaline reaction.
- concentration of the agent having an alkaline reaction influences the necessary time during which the print is exposed to the air passage to such an extent that with the increasing concentration of alkali the required time of residence of the printed material in the air is reduced. If, for example, cc. of sodium hydroxide solution (38 B.) are used per liter of padding liquor, the required minimum time of exposing the print to the air passage is about 10 seconds. As a rule, the minimum time of exposing the print to an air passage is between 1 and 5 minutes. In general, it is preferable to adjust the concentration of alkali in the padding liquor in such a way that the pH-value is be tween about 13 and 14. The optimum concentration of alkali and the time of residence of the printed material in the air must be regulated in each case according to the reactive dyestufi' used.
- Suitable thickening agents are neutral thickening agents or thickeners having a weakly alkaline reaction such as, for example, alginates, different types of gum, or alkyl celluloses.
- EXAMPLE 1 40 parts of the dyestuff of the formula I SOaNa are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water.
- the printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 30 seconds at C.
- sodium hydroxide solution 38 B.
- 150 parts of sodium carbonate 180 parts of sodium chloride
- 50 parts of potassium carbonate made up to 1000 parts by volume with water
- the print thus obtained is then rinsed for about 10 minutes with cold water, treated for 3 minutes with Water which contains 3 parts of a complex forming agent on the base of a polymeric sodium meta-phosphate per 1000 parts by volume, subsequently soaped for about 10 minutes with an aqueous solution of 1% strength of a synthetic detergent (sodium salt of the condensation product of oleic acid and N-methyl taurine) and finally rinsed and dried.
- a synthetic detergent sodium salt of the condensation product of oleic acid and N-methyl taurine
- a yellow print is obtained having a good fastness to light and wet processing.
- EXAMPLE 2 40 parts of the dyestuff of the formula NaOaS SOGNQ SOzCH2OH20SO3Na are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of parts of the sodium salt of metal-nitrobenzene sulfonic acid the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a staple fibre fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 1 minute at C.
- EXAMPLE 3 40 parts of the dyestuff described in Example 2 are mixed according to the method of the said example to form a printing paste.
- This printing paste is printed on a staple fibre fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 3 minutes at 18 C.
- SO Na are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 450 parts of an aqueous methyl cellulose of 3%. After addition of 10 parts of the sodium salt of meta-nitrobenzene sulfonic acid the whole is made up to 1000 parts by the addition of parts of water.
- the printing paste prepared in such a way is then printed on a staple fibre fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 1 minute at 15 C.
- EXAMPLE 5 50 parts of the dyestulf of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 450 parts of an aqueous methyl cellulose of 3%. After addition of 10 parts of the sodium salt of meta-nitrobenzene sulfonic acid the whole is made up to 1000 parts by the addition of parts of water. The printing paste prepared in such a way is then printed on a cotton fabric. After drying, the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (3 8 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water and then exposed to an air passage for 3 minutes at 22 C.
- sodium hydroxide solution 3 8 B.
- EXAMPLE 6 60 parts of the dyestuff of the formula NH: OH OH are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium metaphosphate per 1000 parts of thickener. After addition of parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 130 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (3 8 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000' parts by volume with water and then exposed to an air passage for 1 minute at 20 C.
- a liquor consisting of 100 parts by volume of sodium hydroxide solution (3 8 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000' parts by volume with water and then exposed to an air passage for 1 minute at 20 C.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 3 minutes at 18 C.
- SOsNB COONa SOg-CHz-CHrO-SOgNa are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 500 parts of an aqueous gum thickener of 2.5%. After addition of 10 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 80 parts of Water.
- the printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of 100' parts by volume of sodium hydroxide solution (38 B.), 150
- EXAMPLE 9 40 parts of the dyestulf of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alignate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium metaphosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 25 C.
- sodium hydroxide solution 38 B.
- parts of sodium carbonate parts of sodium carbonate
- EXAMPLE 10 40 parts of the dyestuff of the formula SOsNa are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 par-ts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 23 C.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 10 minutes at 23 C.
- EXAMPLE 12 40 parts of the dyestuff of the formula Naoas are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 22 C.
- EXAMPLE 13 40 parts of the dyestufi of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for minutes at 22 C.
- the printing paste prepared in such a way is then printed on a staple fibre fabric by means of a cylinder printing machine. After drying, the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 3 minutes at 20 C.
- sodium hydroxide solution 38 B.
- parts of sodium carbonate parts of sodium chloride
- 50 parts of potassium carbonate made up to 1000 parts by volume with water
- EXAMPLE 15 40 parts of the dyestuif of the formula SOaNa OH Q F NaOaS NH-CO H- H2 are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of parts of water. The printing paste prepared in such a way is then printed on a linen fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 10 seconds at 15 C.
- EMMPLE 16 40 parts of the dyestuff of the formula GFz-CF,
- EXAMPLE 17 40 parts of the dyestuff of the formula are dissolved in 300 parts of hot water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the whole is made up to 1000 parts by the addition of 195 parts of Water. The printing paste prepared in such a way is then printed on a cotton fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 1 minute at 22 C.
- EXAMPLE 18 40 parts of the dyestuff of the formula SOaNa are dissolved in 300 parts of hot Water after mixing with 50 parts of urea and introduced into 400 parts of an aqueous alginate thickener of 4% which contains 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After addition of 15 parts of the sodium salt of meta-nitrobenzene sulfonic acid, the Whole is made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a Way is then printed on a cotton fabric by means of a cylinder printing machine.
- the printed fabric is padded with a liquor consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 5 minutes at 20 C.
- the printed fabric is padded with a liquor consisting of parts by volume of sodium hydroxide solution (38 B.), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with Water, and then exposed to an air passage for 10 minutes at 20 C.
- sodium hydroxide solution 38 B.
- parts of sodium carbonate parts of sodium carbonate
- a process for producing fast prints on textile materials of natural or regenerated cellulose fibres which comprises printing on said textile materials a printing paste containing a neutral to weakly alkaline thickening agent, water and an organic dyestuif containing at least one ,B-hydroxyethylsulfone sulfuric acid ester group, vinylsulfonyl group, dichlorotriazine group, ethionylamino group, N-alkyl-ethionylamino group, 2,2,3,3-tetrafluorocyclobutane 1 carbonylamino group, 2-fluoro-2- chloro 3,3 difiuorocyclobutane-1-carbonylamino group, 2,2,3,3-difluorocyclobutane-l-carbonylamino group, 2,2, 3,3-tetrafiuorocyclobutane-acroylamino group, vinylsulfonylamino group or 2,3-dichloroquinoxaline residue,
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF0045848 | 1965-04-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3442601A true US3442601A (en) | 1969-05-06 |
Family
ID=7100709
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US541129A Expired - Lifetime US3442601A (en) | 1965-04-17 | 1966-04-08 | Process for printing textile materials of natural or regenerated cellulose with reactive dyestuffs |
Country Status (9)
Country | Link |
---|---|
US (1) | US3442601A (fr) |
AT (1) | AT265197B (fr) |
BE (1) | BE679670A (fr) |
CH (2) | CH539766A4 (fr) |
DE (1) | DE1469722C3 (fr) |
FR (1) | FR1476297A (fr) |
GB (1) | GB1135669A (fr) |
NL (1) | NL6604851A (fr) |
SE (1) | SE315867B (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111535059A (zh) * | 2020-05-27 | 2020-08-14 | 山东黄河三角洲纺织科技研究院有限公司 | 一种人造纤维素纤维面料的数码印花工艺 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH657865A5 (de) * | 1983-12-20 | 1986-09-30 | Ciba Geigy Ag | Reaktivfarbstoffe und deren herstellung. |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3334961A (en) * | 1961-02-24 | 1967-08-08 | Hoechst Ag | Process for dyeing or printing materials of fibrous structure containing cellulose |
-
1965
- 1965-04-17 DE DE1469722A patent/DE1469722C3/de not_active Expired
-
1966
- 1966-04-08 US US541129A patent/US3442601A/en not_active Expired - Lifetime
- 1966-04-12 NL NL6604851A patent/NL6604851A/xx unknown
- 1966-04-14 CH CH539766D patent/CH539766A4/xx unknown
- 1966-04-14 SE SE5070/66A patent/SE315867B/xx unknown
- 1966-04-14 CH CH539766A patent/CH501102A/de not_active IP Right Cessation
- 1966-04-15 AT AT358066A patent/AT265197B/de active
- 1966-04-18 FR FR57969A patent/FR1476297A/fr not_active Expired
- 1966-04-18 GB GB16909/66A patent/GB1135669A/en not_active Expired
- 1966-04-18 BE BE679670D patent/BE679670A/xx not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3334961A (en) * | 1961-02-24 | 1967-08-08 | Hoechst Ag | Process for dyeing or printing materials of fibrous structure containing cellulose |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111535059A (zh) * | 2020-05-27 | 2020-08-14 | 山东黄河三角洲纺织科技研究院有限公司 | 一种人造纤维素纤维面料的数码印花工艺 |
Also Published As
Publication number | Publication date |
---|---|
DE1469722B2 (de) | 1974-10-31 |
SE315867B (fr) | 1969-10-13 |
FR1476297A (fr) | 1967-04-07 |
BE679670A (fr) | 1966-10-18 |
CH539766A4 (fr) | 1970-09-15 |
DE1469722C3 (de) | 1975-06-12 |
AT265197B (de) | 1968-09-25 |
DE1469722A1 (de) | 1970-01-08 |
GB1135669A (en) | 1968-12-04 |
NL6604851A (fr) | 1966-10-18 |
CH501102A (de) | 1970-09-15 |
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