US2234905A - Dyeing of cellulosic textile - Google Patents
Dyeing of cellulosic textile Download PDFInfo
- Publication number
- US2234905A US2234905A US2234905DA US2234905A US 2234905 A US2234905 A US 2234905A US 2234905D A US2234905D A US 2234905DA US 2234905 A US2234905 A US 2234905A
- Authority
- US
- United States
- Prior art keywords
- solution
- formaldehyde
- cyanamide
- dyeing
- materials
- 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
- 239000004753 textile Substances 0.000 title description 18
- 238000004043 dyeing Methods 0.000 title description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 64
- 239000000243 solution Substances 0.000 description 58
- 239000000463 material Substances 0.000 description 42
- XZMCDFZZKTWFGF-UHFFFAOYSA-N carbodiimide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 28
- 239000002253 acid Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000000835 fiber Substances 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 229920002301 Cellulose acetate Polymers 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N Thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 210000002268 Wool Anatomy 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000002035 prolonged Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- ZJHHPAUQMCHPRB-UHFFFAOYSA-N urea urea Chemical compound NC(N)=O.NC(N)=O ZJHHPAUQMCHPRB-UHFFFAOYSA-N 0.000 description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N Ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M CHEMBL593252 Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- RSNSKUBBVCGSND-QZQOTICOSA-L E128 Chemical compound OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1\N=N\C1=CC=CC=C1 RSNSKUBBVCGSND-QZQOTICOSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N cyanoguanidine Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000001627 detrimental Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M isothiocyanate Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- -1 methylol compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 235000012739 red 2G Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
Images
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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
- D06P5/225—Aminalization of cellulose; introducing aminogroups into cellulose
Definitions
- This invention relates to the dyeing of cellulosic textile materials.
- cellulosic fibres can be dyed by acid dyestuffs ii the fibres have been pretreated with various materials.
- various materials such as amines and ammonium bases.
- treatment with solutions containing urea or thiourea mixed with or precondensed with aldehyde followed by heating to obtain condensation products on the fibres has also been proposed for this purpose.
- the methylol compounds of urea or thiourea do not possess sufllcient chemical aflinity for acid dyes to be useful technically for dyeing purposes.
- the process for improving the dyeing properties of cellulosic textile materials comprises incorporating in the said materials a product obtained by causing cyanamlde and formaldehyde to react under acid or neutral conditions.
- One method oi carrying out the said process comprises impregnating the said cellulosic textile materials with a solution, obtained by mixing in the cold solutions of cyanamide and formaldehyde, which solution is maintained slightly acid. The best results are obtained when the pH value of the solution lies between 5.0 and 6.5. After impregnation the material is dried and heated to ensure reaction between the cyanamide and formaldehyde.
- the cyanamide and formaldehyde may be partially or wholly precondensed by heating the mixed solution at raised temperatures, for example to centrigrade, under slightly acid conditions, preferably at a pH value of 5.0.
- the material after impregnation with the solution thus obtained is dried and heated to complete the reaction between cyanamide and formaldehyde in the material.
- the process according to the present invention may be carried out by incorporating in the cellulosic solution, for example, viscose, which is to be used for forming cellulosic threads, the product which is precipitated on prolonged heating above 60 centigrade of a solution'of the initially slightly acid. solution obtained by mixing solutions of cyanamide and formaldehyde.
- An intensifier or any other useful compound for example ammonium thiocyenate, which greatly increases the affinity of the textile material ior certain direct dyestuffs may be added to the solutions used for the treatment of such materials. If these lntensifiers or other compounds are of a basic nature, for example,triethylamine, then it is necessary to neutralise them before they are incorporated in the treating solution.
- the cellulosic materials obtained according to the present invention have an increased afilnity for many classes of dyestuffs which may be applied to such materials, including direct cotton, sulphur, vat, azolc, basic and acid dyestuils, and also those dyestufi's specially evolved for the dyeing of cellulose acetate or the like cellulose derivatives. Moreover, the fastness to washing processes of the resulting dyed material is greatly improved.
- Example 1 12 parts of crude calcium cyanamide are extracted with 36 parts of water at from 35 to 45 centigrade for 30 minutes and subsequently filtered and neutralised with strong sulphuric acid.
- the calcium sulphate is filtered ofl.
- To the filtrate are added 15 parts of commercial formaldehyde solution (containing 40 per cent of formaldehyde), 1 part of ammonium thiocyanate and 15 parts of water.
- Viscose staple fibre is steeped in this solution, squeezed out and centlfuged to twice its original weight. It is then dried by known processes and finally heated for twenty minutes at centigrade. It is then dyed at the boil for one hour with l per cent oi azo-geranine 2 G. S. and 2 per cent of sulphuric acid.
- a rich scarlet shade is imparted to the fibre comparable with that developed by the same dyestufi on wool.
- Example 2 A solution, containing 4 per cent of cyanamide and 8 per cent of formaldehyde, at a pH value of 5.0, is heated at 80 centigrade until a voluminous white precipitate is formed. The precipitate is filtered off, washed anddried. It is then dispersed in acetone and added to a cellulose acetate spinning solution. The cellulose acetate yarn obtained from this solution is then dyed at 80 centigrade for one hour with 2 per cent anogeranine 2 G. 8., and 2 per cent of formic acid. It can also be dyed under the same conditions with erio fast cyanine S concentrated.
- Example 3 monium thiocyanate at a pH value of 0.0.
- Example 4 5 parts of a per cent solution of cyanamide are added to 0 parts of 40 per cent formaldehyde solution and the resulting solution is heated at 95' centigrade for 3 minutes. After rapidly cooling to room temperature the solution is diluted with parts of water and the solution so obtained used to impregnate staple fibre. The impregnated staple fibre is hydro-extracted and dried at centizrade the temperature then bein: raised to centigrade for one hour. The treated fibre is dyed at the boil for oi'an hour in a dyebath containing 2 per cent of arc-geranine 2 G. 8. and 2 per cent of formic acid on the weight of the fibre using a liquor to yarn ratio of 40 to 1. The dyebath is exhausted and a full shade developed on the fibre.
- a process for improving the dyeing properties of cellulosic textile materials which comprises incorporating in the said materials a product obtained by causing cyanamide and formaldehyde to react in a solution the pH value of which initially lies between 5.0 and 5.5.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Description
Patented Mar. 11, 1941 UNITED STATES prams OF CELLULOSIC TEXTILE MATERIALS Ernest Edward Tallis,
Coventry, England, as-
signor to Courtaulds, Limited, London, England, a British company No Drawing. Application November 19, 1938, Se-
rial No. 241,460. In Great Britain November 4 Claims.
This invention relates to the dyeing of cellulosic textile materials.
It is well known that it is not ordinarily possible to dye cellulosic materials such as cotton, rayon, linen or the like with acid dyestuffs such as are commonly used for the dyeing of wool and the like animal fibres.
It is also known, however, that such cellulosic fibres can be dyed by acid dyestuffs ii the fibres have been pretreated with various materials. For example it has been proposed to dye such cellulosic fibres after treatment with nitrogenous materials, such as amines and ammonium bases. Treatment with solutions containing urea or thiourea mixed with or precondensed with aldehyde followed by heating to obtain condensation products on the fibres has also been proposed for this purpose. It has also been stated that the methylol compounds of urea or thiourea do not possess sufllcient chemical aflinity for acid dyes to be useful technically for dyeing purposes. In view of this a proposal has been made to use the initial condensation products of formaldehyde with dicyandiamide, guanidine or heat-treated urea, which while not detrimental to the good textile properties of the fibre lend it a pronounced amnity for acid dyestufis and in some cases for basic dyestuffs.
In British Patent No. 319,822 a process of manui'acturing new compounds by the interaction of cyanamide with formaldehyde is described and it is stated that the properties of the product obtained by condensing under acid conditions are different from those of the product obtained by condensing under alkaline conditions.
According to the present invention the process for improving the dyeing properties of cellulosic textile materials, comprises incorporating in the said materials a product obtained by causing cyanamlde and formaldehyde to react under acid or neutral conditions.
One method oi carrying out the said process, comprises impregnating the said cellulosic textile materials with a solution, obtained by mixing in the cold solutions of cyanamide and formaldehyde, which solution is maintained slightly acid. The best results are obtained when the pH value of the solution lies between 5.0 and 6.5. After impregnation the material is dried and heated to ensure reaction between the cyanamide and formaldehyde. The cyanamide and formaldehyde may be partially or wholly precondensed by heating the mixed solution at raised temperatures, for example to centrigrade, under slightly acid conditions, preferably at a pH value of 5.0. The material after impregnation with the solution thus obtained is dried and heated to complete the reaction between cyanamide and formaldehyde in the material.
Alternatively, the process according to the present invention, may be carried out by incorporating in the cellulosic solution, for example, viscose, which is to be used for forming cellulosic threads, the product which is precipitated on prolonged heating above 60 centigrade of a solution'of the initially slightly acid. solution obtained by mixing solutions of cyanamide and formaldehyde.
An intensifier or any other useful compound, for example ammonium thiocyenate, which greatly increases the affinity of the textile material ior certain direct dyestuffs may be added to the solutions used for the treatment of such materials. If these lntensifiers or other compounds are of a basic nature, for example,triethylamine, then it is necessary to neutralise them before they are incorporated in the treating solution.
The cellulosic materials obtained according to the present invention have an increased afilnity for many classes of dyestuffs which may be applied to such materials, including direct cotton, sulphur, vat, azolc, basic and acid dyestuils, and also those dyestufi's specially evolved for the dyeing of cellulose acetate or the like cellulose derivatives. Moreover, the fastness to washing processes of the resulting dyed material is greatly improved.
The following examples illustrate methods of carrying the present invention into effect, although the invention is not restricted to these examples.
Example 1 12 parts of crude calcium cyanamide are extracted with 36 parts of water at from 35 to 45 centigrade for 30 minutes and subsequently filtered and neutralised with strong sulphuric acid. The calcium sulphate is filtered ofl. To the filtrate are added 15 parts of commercial formaldehyde solution (containing 40 per cent of formaldehyde), 1 part of ammonium thiocyanate and 15 parts of water. Viscose staple fibre is steeped in this solution, squeezed out and centlfuged to twice its original weight. It is then dried by known processes and finally heated for twenty minutes at centigrade. It is then dyed at the boil for one hour with l per cent oi azo-geranine 2 G. S. and 2 per cent of sulphuric acid. A rich scarlet shade is imparted to the fibre comparable with that developed by the same dyestufi on wool.
2 Example 2 A solution, containing 4 per cent of cyanamide and 8 per cent of formaldehyde, at a pH value of 5.0, is heated at 80 centigrade until a voluminous white precipitate is formed. The precipitate is filtered off, washed anddried. It is then dispersed in acetone and added to a cellulose acetate spinning solution. The cellulose acetate yarn obtained from this solution is then dyed at 80 centigrade for one hour with 2 per cent anogeranine 2 G. 8., and 2 per cent of formic acid. It can also be dyed under the same conditions with erio fast cyanine S concentrated.
Example 3 monium thiocyanate at a pH value of 0.0. The
\ impregnated yarn is then hydro-extracted, dried and heated at 150 centigrade for 5 minutes. It is then dyed a full shade with 3 per cent coomassie red P. G. 8. (Imperial Chemical Industries) and exhausts the dye bath. Theyarn obtained is also dyed a much fuller shade with indigosol blue I. B. C. than yarn which has not been so treated.
Example 4 5 parts of a per cent solution of cyanamide are added to 0 parts of 40 per cent formaldehyde solution and the resulting solution is heated at 95' centigrade for 3 minutes. After rapidly cooling to room temperature the solution is diluted with parts of water and the solution so obtained used to impregnate staple fibre. The impregnated staple fibre is hydro-extracted and dried at centizrade the temperature then bein: raised to centigrade for one hour. The treated fibre is dyed at the boil for oi'an hour in a dyebath containing 2 per cent of arc-geranine 2 G. 8. and 2 per cent of formic acid on the weight of the fibre using a liquor to yarn ratio of 40 to 1. The dyebath is exhausted and a full shade developed on the fibre.
What I claim is:
i. A process for improving the dyeing properties of cellulosic textile materials which comprises incorporating in the said materials a product obtained by causing cyanamide and formaldehyde to react in a solution the pH value of which initially lies between 5.0 and 5.5.
2. A process asclaimed in claim 1, wherein the materials are impregnated with the solution obtained by the admixture in the cold of solutions of cyanamide and formaldehyde, which solution is maintained slightly acid at a pH value between 5.0 and 6.5, the said materials after impregnation being dried and heated to cause reaction between the cyanamide and formaldehyde.-
3. A process as claimed in claim 1, wherein the materials are impregnated with the solution obtained by heating a solution containing cyanomide and formaldehyde while maintaining the pH value of the solution between 5.0 and 0.5 to give partial or complete precondensation, and are thereafter dried and heated to complete the reaction between the cyanamide and formaldehyde.
4. A process as claimed in claim 1. wherein the product which is precipitated after the prolonged heating above 60 centigrade of a solution of cyanamide and formaldehyde the pH value of which is initially between 5.0 and 6.5, is incorporated in the cellulosic solution from which eellulosic textile threads are produced.
ERNEST EDWARD TALL-IS.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2234905A true US2234905A (en) | 1941-03-11 |
Family
ID=3431793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2234905D Expired - Lifetime US2234905A (en) | Dyeing of cellulosic textile |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2234905A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2440330A (en) * | 1943-08-26 | 1948-04-27 | Celanese Corp | Improving the fastness of dyed organic derivative of cellulose textiles by impregnation with cyanamide |
| US2458397A (en) * | 1943-11-18 | 1949-01-04 | Courtaulds Ltd | Dyeing of nylon fibers by treating with nitrogenous condensation products |
| US2530261A (en) * | 1947-08-22 | 1950-11-14 | Courtaulds Ltd | Fireproofing and creaseproofing of cellulose and protein textiles |
| US2736749A (en) * | 1952-06-10 | 1956-02-28 | Arnold Hoffman & Co Inc | Dye-fixing agents |
| US3066032A (en) * | 1959-05-26 | 1962-11-27 | Kurashiki Rayon Co | Method of making fibers of regenerated cellulose of improved dyeing properties |
| US3245751A (en) * | 1962-05-24 | 1966-04-12 | Montedison Spa | Textile fibers having improved dyeability and method of preparing same |
-
0
- US US2234905D patent/US2234905A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2440330A (en) * | 1943-08-26 | 1948-04-27 | Celanese Corp | Improving the fastness of dyed organic derivative of cellulose textiles by impregnation with cyanamide |
| US2458397A (en) * | 1943-11-18 | 1949-01-04 | Courtaulds Ltd | Dyeing of nylon fibers by treating with nitrogenous condensation products |
| US2530261A (en) * | 1947-08-22 | 1950-11-14 | Courtaulds Ltd | Fireproofing and creaseproofing of cellulose and protein textiles |
| US2736749A (en) * | 1952-06-10 | 1956-02-28 | Arnold Hoffman & Co Inc | Dye-fixing agents |
| US3066032A (en) * | 1959-05-26 | 1962-11-27 | Kurashiki Rayon Co | Method of making fibers of regenerated cellulose of improved dyeing properties |
| US3245751A (en) * | 1962-05-24 | 1966-04-12 | Montedison Spa | Textile fibers having improved dyeability and method of preparing same |
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