US2506020A - Mixture of insoluble aminoanthraquinone dyes - Google Patents

Mixture of insoluble aminoanthraquinone dyes Download PDF

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US2506020A
US2506020A US49292A US4929248A US2506020A US 2506020 A US2506020 A US 2506020A US 49292 A US49292 A US 49292A US 4929248 A US4929248 A US 4929248A US 2506020 A US2506020 A US 2506020A
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Prior art keywords
mixture
parts
anthraquinone
dyeing
amino
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US49292A
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Grossmann Paul
Kern Walter
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BASF Schweiz AG
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Ciba AG
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    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
    • C09B1/325—Dyes with no other substituents than the amino groups
    • 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
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/921—Cellulose ester or ether

Definitions

  • mixtures of dyestuffs are in some cases of advantage for dyeing cellulose esters, for example, artificial silk or staple fibers of lower fatty acids of cellulose, such as cellulose butyrate, cellulose propionate and especially cellulose acetate, and also the corresponding mixed esters.
  • the use of mixtures of dyestuffs is indicated, inter alia, when the dyestuif mixture is required not for producing a desired shade of color but when each of the dyestuffs to be mixed yields dyeings of the same tint or very similar tints, owing to the fact that in many cases such a mixture yields a stronger tint than do the individual pure components of the mixture. This so-called mixture effect varies in strength in difierent instances.
  • the present invention is based on the observation that unexpectedly good dyeings on cellulose esters are obtained by using mixtures of which the dyeing constituents consist mainly of l-(c-hydroxyethyl) amino 4 phenylamino anthraquinone and l methylamino 4 phenylamino- .anthraquinone in finely divided form.
  • cellulose esters to be dyed by the process of this invention there may be used the known esters of cellulose with aliphatic acids of low molecular weight mentioned above.
  • the fibers of some cellulose ethers and of superpolyamides, superpolyurethanes and superpolyesters are to be regarded as equivalents of fibers of cellulose esters, owing to their similar properties.
  • the individual components of the mixture namely 1 (fl-hydroxyethyl) -amino 4 phenylamlno anthraquinone and 1 methylamino- 4-phenylamino-anthraquinone, are in themselves known and can be obtained in various ways. It is of advantage to use them in the present process in a pure or relatively pure state. They may be converted in known manner into a finely divided condition prior to the dyeing process, for example, by grinding with a dispersing agent such as sulfite cellulose waste liquor, advantagefuric acid.
  • a dispersing agent such as sulfite cellulose waste liquor, advantagefuric acid.
  • the two components may be mixed together before or during the preparation of the dyebath.
  • the relative proportions of the components may vary within fairly wide limits, but it is of advantage to use not less than 20 per cent, preferably 25-50 per cent, of the component which is present in lower proportion.
  • Dyeing may be carried out in the usual manner, for example, in aqueous dispersion with the addition of a wetting or dispersing agent such as a soap, an N-benzyl- -heptadecyl-benzimidazole sulfonic acid, a condensation product of taurine or methyl-taurine with a fatty acid, or the like.
  • a wetting or dispersing agent such as a soap, an N-benzyl- -heptadecyl-benzimidazole sulfonic acid, a condensation product of taurine or methyl-taurine with a fatty acid, or the like.
  • a dyestuff preparation which contains the two components mentioned above in the desired relative proportions and in a state of fine dispersion and also contains a wetting or dispersing agent such as sulfite cellulose waste liquor, salts of condensation products from formaldehyde and naphthalene sulfonic acids, naphthenic acid salts, if desired with the addition of wetting agents, such as are mentioned above.
  • a wetting or dispersing agent such as sulfite cellulose waste liquor, salts of condensation products from formaldehyde and naphthalene sulfonic acids, naphthenic acid salts, if desired with the addition of wetting agents, such as are mentioned above.
  • Example 1 4 parts of 1 ([3 hydroxyethyl) amino- 4 phenylamino-anthraquinone and 4 parts of 1 methylamino-4-phenylamino anthraquinone are dissolved in 50 parts of sulfuric acid of per cent. strength. The solution is introduced into a mixture of parts of ice, 240 parts of water and 55 parts of ammonia solution of 25 per cent. strength, stirred well and filtered. The filter residue is washed neutral and ground with about 12 parts of dried sulfite cellulose waste liquor and the necessary quantity of water to form a dyestuif paste containing about 10 per cent. of the dyestufi mixture.
  • the paste so obtained produces on cellulose acetate artificial silk blue dyeings of great purity. It enables dark blue tints to be obtained which are darker than those obtainable with the individual components of the mixture or can be obtained therewith only by using a very much greater quantity of dyestuff and then not in the same degree of purity.
  • Example 2 By using in the procedure of Example 1, 6 parts, instead of 4 parts, of l-(p-hydroxethyl)-amino- 4-phenylamino-anthraquinone and 2 parts, instead of 4 parts, of l-methylamino--phenylamino-anthraquinone, there are obtained similar 3 results which approach closely the good results obtained in Example 1.
  • Example 3 10 parts of a paste of 10 per cent strength of finely dispersed l-(fl-hydroxyethyl) amino-ephenylaminoanthraquinone and 10 parts of a paste of 10 per cent. strength of l-methylamino- 4-phenylamino-anthraquinone are introduced into a solution of 6 parts of the sodium salt of N- benzyl,u-heptadecyl benzimidazole disulfonic acid in 200 parts of water at 30 0., and 3000 parts of water at 40 C. are added while stirring well. 100 parts of well wetted cellulose acetate artificial sill: are entered at 40 C., the temperature is raised to 80 C. in the course of hour, and dyeing is carried on at that temperature for one hour. The artificial silk is then rinsed and finished in the usual manner. A deep blue dyeingis obtained of great purity.
  • Example 4 The procedure is the same as that described in Example 3, except that 20 parts of a dyestuii paste are used containing 10 per cent. of the dyestuii mixture and prepared as described in Example l or 2. Very similar results are ob tained.
  • the amount of dispersing agent contained in the dyestuii preparations is not critical and may range from one tenth to many times the combined weight of the two dyestuffs.
  • the dispersing agent may be omitted altogether if care is taken that, nevertheless, the dyebath prepared with the prepara tion contains the dyestuffs in finely dispersed condition.
  • the dyestuff preparations may be aqueous pastes or thinly liquid dispersions or they may be dried, for example in an atomizer, especially if the amount of dispersing agent is not too low.
  • acetate rayon dyes other than those specified above, may
  • a dyestuff preparation in which the dyeing constituent consists mainly of a mixture or" 1-([3- hydroxyethyl) aminol-phenylamino anthraquinone and 1-methylamino-4-phenylaminoanthraquinone in a finely divided and dispersible condition and in relative proportions ranging from about 4:1 to 1:4, the said anthraquinone compounds being substantially free from impurities possessing afiinity for acetate rayon.
  • a dyestuff preparation consisting of Water, a dispersing agent, and approximately equal quantities or l-(fi-hydrcxyethyl) -amino-4-phenylaminoanthraquinone and l-methyl amino-ephenylaminoanthraquinone in a finely divided and dispersible condition.

Description

Patented May 2, 1950 MIXTURE OF INSOLUBLE AMINO- ANTHRAQUINONE DYES Paul Grossmann, Binningen, and Walter Kern, Sissach, Switzerland, assignors to Ciba Limited,
a Swiss firm No Drawing. Application September 14, 1948, Se-
rial No. 49,292. In Switzerland November 26,
Claims.
It is known that mixtures of dyestuffs are in some cases of advantage for dyeing cellulose esters, for example, artificial silk or staple fibers of lower fatty acids of cellulose, such as cellulose butyrate, cellulose propionate and especially cellulose acetate, and also the corresponding mixed esters. The use of mixtures of dyestuffs is indicated, inter alia, when the dyestuif mixture is required not for producing a desired shade of color but when each of the dyestuffs to be mixed yields dyeings of the same tint or very similar tints, owing to the fact that in many cases such a mixture yields a stronger tint than do the individual pure components of the mixture. This so-called mixture effect varies in strength in difierent instances. It naturally also occurs when by-products are formed in the manufacture of a single dyestufi and the by-products remain in the final dyestuif. Especially pronounced mixture effects, that is to say those in which the resulting mixed dyeing is very considerably stronger than the dyeings obtainable with the stronger-dyeing component of the mixture, are rare. Moreover, a dyeing of enhanced purity is not to be expected by the use of mixtures, and in some cases, as would be expected, the mixed dyeing is more or less markedly dull.
The present invention is based on the observation that unexpectedly good dyeings on cellulose esters are obtained by using mixtures of which the dyeing constituents consist mainly of l-(c-hydroxyethyl) amino 4 phenylamino anthraquinone and l methylamino 4 phenylamino- .anthraquinone in finely divided form.
As cellulose esters to be dyed by the process of this invention there may be used the known esters of cellulose with aliphatic acids of low molecular weight mentioned above. The fibers of some cellulose ethers and of superpolyamides, superpolyurethanes and superpolyesters are to be regarded as equivalents of fibers of cellulose esters, owing to their similar properties.
The individual components of the mixture, namely 1 (fl-hydroxyethyl) -amino 4 phenylamlno anthraquinone and 1 methylamino- 4-phenylamino-anthraquinone, are in themselves known and can be obtained in various ways. It is of advantage to use them in the present process in a pure or relatively pure state. They may be converted in known manner into a finely divided condition prior to the dyeing process, for example, by grinding with a dispersing agent such as sulfite cellulose waste liquor, advantagefuric acid.
The two components may be mixed together before or during the preparation of the dyebath. The relative proportions of the components may vary within fairly wide limits, but it is of advantage to use not less than 20 per cent, preferably 25-50 per cent, of the component which is present in lower proportion.
Dyeing may be carried out in the usual manner, for example, in aqueous dispersion with the addition of a wetting or dispersing agent such as a soap, an N-benzyl- -heptadecyl-benzimidazole sulfonic acid, a condensation product of taurine or methyl-taurine with a fatty acid, or the like.
It is also of advantage to make a dyestuff preparation which contains the two components mentioned above in the desired relative proportions and in a state of fine dispersion and also contains a wetting or dispersing agent such as sulfite cellulose waste liquor, salts of condensation products from formaldehyde and naphthalene sulfonic acids, naphthenic acid salts, if desired with the addition of wetting agents, such as are mentioned above.
The following examples illustrate the invention, the parts being by weight:
Example 1 4 parts of 1 ([3 hydroxyethyl) amino- 4 phenylamino-anthraquinone and 4 parts of 1 methylamino-4-phenylamino anthraquinone are dissolved in 50 parts of sulfuric acid of per cent. strength. The solution is introduced into a mixture of parts of ice, 240 parts of water and 55 parts of ammonia solution of 25 per cent. strength, stirred well and filtered. The filter residue is washed neutral and ground with about 12 parts of dried sulfite cellulose waste liquor and the necessary quantity of water to form a dyestuif paste containing about 10 per cent. of the dyestufi mixture.
The paste so obtained produces on cellulose acetate artificial silk blue dyeings of great purity. It enables dark blue tints to be obtained which are darker than those obtainable with the individual components of the mixture or can be obtained therewith only by using a very much greater quantity of dyestuff and then not in the same degree of purity.
Example 2 By using in the procedure of Example 1, 6 parts, instead of 4 parts, of l-(p-hydroxethyl)-amino- 4-phenylamino-anthraquinone and 2 parts, instead of 4 parts, of l-methylamino--phenylamino-anthraquinone, there are obtained similar 3 results which approach closely the good results obtained in Example 1.
Similar results are obtained by using 2 parts of 1 -(,8-hydroxyethy1) amino-e-phenylaminoanthraquinone and 6 parts of l-methyiaminoiphenylamino-anthraquinone.
Example 3 10 parts of a paste of 10 per cent strength of finely dispersed l-(fl-hydroxyethyl) amino-ephenylaminoanthraquinone and 10 parts of a paste of 10 per cent. strength of l-methylamino- 4-phenylamino-anthraquinone are introduced into a solution of 6 parts of the sodium salt of N- benzyl,u-heptadecyl benzimidazole disulfonic acid in 200 parts of water at 30 0., and 3000 parts of water at 40 C. are added while stirring well. 100 parts of well wetted cellulose acetate artificial sill: are entered at 40 C., the temperature is raised to 80 C. in the course of hour, and dyeing is carried on at that temperature for one hour. The artificial silk is then rinsed and finished in the usual manner. A deep blue dyeingis obtained of great purity.
Example 4 The procedure is the same as that described in Example 3, except that 20 parts of a dyestuii paste are used containing 10 per cent. of the dyestuii mixture and prepared as described in Example l or 2. Very similar results are ob tained.
It is to be understood that the amount of dispersing agent contained in the dyestuii preparations is not critical and may range from one tenth to many times the combined weight of the two dyestuffs. The dispersing agent may be omitted altogether if care is taken that, nevertheless, the dyebath prepared with the prepara tion contains the dyestuffs in finely dispersed condition.
If desired, the dyestuff preparations may be aqueous pastes or thinly liquid dispersions or they may be dried, for example in an atomizer, especially if the amount of dispersing agent is not too low.
It is further to be understood that acetate rayon dyes, other than those specified above, may
be present as impurities or purposely added to the preparations in minor amounts, for example if not all of the beneficial effects of the present invention are required, or if the dyes added do not interfere therewith.
What we claim is:
1. A dyestuff preparation in which the dyeing constituent consists mainly of a mixture or" 1-([3- hydroxyethyl) aminol-phenylamino anthraquinone and 1-methylamino-4-phenylaminoanthraquinone in a finely divided and dispersible condition and in relative proportions ranging from about 4:1 to 1:4, the said anthraquinone compounds being substantially free from impurities possessing afiinity for acetate rayon.
2. A dyestuii preparation containing a dispersing agent in which the dyeing constituent consists mainly of a mixture of l-(B-hydroxyethyl) amino 4 phenylaminoanthraquinone and 1- methyl-amino-4-phenylaminoanthraqulnone in a finely divided and dispersible condition and in relative proportions ranging from about 4:1 to 1:4.
3. A dyestuif preparation containing a dispers- 3 ing agent in which the dyeing constituent consists of a mixture of lJB-hydroxyethyl) -aminophenylaminoanthraquinone and 1methyl-amino-' i-phenylaminoanthraquinone in a finely divided and dispersible condition and in approximately equal quantities.
A dyestuif preparation containing a dispersing agent in which the dyeing constituent consists of a mixture of l-(B-hydroxyethyl) -amino- 4 phenylaminoanthraquinone and l methylaminoA-phenylaminoanthraquinone in a finely divided and dispersible condition and in relative proportions ranging from about 4:1 to 1:4, the said anthraquinone compounds being substantial- 1y free from impurities possessing affinity for acetate rayon.
5. A dyestuff preparation consisting of Water, a dispersing agent, and approximately equal quantities or l-(fi-hydrcxyethyl) -amino-4-phenylaminoanthraquinone and l-methyl amino-ephenylaminoanthraquinone in a finely divided and dispersible condition.
PAUL GROSSMANN. WALTER KERN.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,967,772 Grossmann July 24, 1934 2,060,186 Felix Nov. 10, 1936 2,272,294 Finlayson Feb. 10, 1942 2,342,191 Grossmann Feb. 22, 1944

Claims (1)

1. A DYESTUFF PREPARATION IN WHICH THE DYEING CONSTITUENT CONSISTS MAINLY OF A MIXTURE OF 1-(BHYDROXYETHYL) - AMINO-4-PHENYLAMINO - ANTHRAQUINONE AND 1-METHYLAMINO-4-PHENYLAMINOANTHRAQUINONE IN A FINELY DIVIDED AND DISPERSIBLE CONDITION AND IN RELATIVE PROPORTIONS RANGING FROM ABOUT 4:1 TO 1:4, THE SAID ANTHRAQUINONE COMPOUNDS BEING SUBSTANTIALLY FREE FROM IMPURITIES POSSESSING AFFINITY FOR ACETATE RAYON.
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2768183A (en) * 1954-08-04 1956-10-23 Gen Aniline & Film Corp Anthraquinone dyestuffs
US2827356A (en) * 1952-10-20 1958-03-18 Celanese Corp Anthraquinone dyestuffs
US2888312A (en) * 1952-08-28 1959-05-26 Ciba Ltd Vat dyestuff mixtures
US2894800A (en) * 1954-01-26 1959-07-14 Saul & Co Dyestuff mixtures
US2967752A (en) * 1958-05-30 1961-01-10 Sandoz Ltd Blue disperse dyestuffs of the anthraquinone series
US2967754A (en) * 1958-05-28 1961-01-10 Sandoz Ag Disperse dyestuffs of the anthraquinone series
US3210345A (en) * 1961-07-03 1965-10-05 Ici Ltd Phthalocyanine dyestuffs
US3264052A (en) * 1962-01-05 1966-08-02 Ciba Ltd Process for dyeing polyester fibers
US3520648A (en) * 1966-12-22 1970-07-14 Geigy Ag J R Process for dyeing organic polyester fibers and composite anthraquinone preparations therefor
US3755201A (en) * 1971-07-26 1973-08-28 Colgate Palmolive Co Laundry product containing mixed dye bluing agents
US3881865A (en) * 1972-06-02 1975-05-06 Ici Ltd Anthraquinone dyestuff mixtures
US3989449A (en) * 1969-03-04 1976-11-02 L. B. Holliday & Co. Limited Dyestuff compositions
WO2018177652A1 (en) * 2017-03-29 2018-10-04 Huntsman Advanced Materials (Switzerland) Gmbh Process for printing cellulose containing textile fibre material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1967772A (en) * 1932-09-20 1934-07-24 Chem Ind Basel 1-alkylamino-4-arylaminoanthraquinones and process of making such products
US2060186A (en) * 1932-10-15 1936-11-10 Soc Of Chemical Ind Dyeing of acetate artificial silk
US2272294A (en) * 1938-07-23 1942-02-10 Celanese Corp Laminated materials
US2342191A (en) * 1939-06-10 1944-02-22 Soc Of Chemical Ind Dyeing and printing cellulose esters and ethers with amino-anthraquinone dyes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1967772A (en) * 1932-09-20 1934-07-24 Chem Ind Basel 1-alkylamino-4-arylaminoanthraquinones and process of making such products
US2060186A (en) * 1932-10-15 1936-11-10 Soc Of Chemical Ind Dyeing of acetate artificial silk
US2272294A (en) * 1938-07-23 1942-02-10 Celanese Corp Laminated materials
US2342191A (en) * 1939-06-10 1944-02-22 Soc Of Chemical Ind Dyeing and printing cellulose esters and ethers with amino-anthraquinone dyes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888312A (en) * 1952-08-28 1959-05-26 Ciba Ltd Vat dyestuff mixtures
US2827356A (en) * 1952-10-20 1958-03-18 Celanese Corp Anthraquinone dyestuffs
US2894800A (en) * 1954-01-26 1959-07-14 Saul & Co Dyestuff mixtures
US2768183A (en) * 1954-08-04 1956-10-23 Gen Aniline & Film Corp Anthraquinone dyestuffs
US2967754A (en) * 1958-05-28 1961-01-10 Sandoz Ag Disperse dyestuffs of the anthraquinone series
US2967752A (en) * 1958-05-30 1961-01-10 Sandoz Ltd Blue disperse dyestuffs of the anthraquinone series
US3210345A (en) * 1961-07-03 1965-10-05 Ici Ltd Phthalocyanine dyestuffs
US3264052A (en) * 1962-01-05 1966-08-02 Ciba Ltd Process for dyeing polyester fibers
US3520648A (en) * 1966-12-22 1970-07-14 Geigy Ag J R Process for dyeing organic polyester fibers and composite anthraquinone preparations therefor
US3989449A (en) * 1969-03-04 1976-11-02 L. B. Holliday & Co. Limited Dyestuff compositions
US3755201A (en) * 1971-07-26 1973-08-28 Colgate Palmolive Co Laundry product containing mixed dye bluing agents
US3881865A (en) * 1972-06-02 1975-05-06 Ici Ltd Anthraquinone dyestuff mixtures
WO2018177652A1 (en) * 2017-03-29 2018-10-04 Huntsman Advanced Materials (Switzerland) Gmbh Process for printing cellulose containing textile fibre material

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