CA1110011A - Modifications of mixtures of azo dyestuffs stable under dyeing conditions - Google Patents
Modifications of mixtures of azo dyestuffs stable under dyeing conditionsInfo
- Publication number
- CA1110011A CA1110011A CA287,268A CA287268A CA1110011A CA 1110011 A CA1110011 A CA 1110011A CA 287268 A CA287268 A CA 287268A CA 1110011 A CA1110011 A CA 1110011A
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- Prior art keywords
- aniline
- temperature
- mole
- cyanethyl
- stable under
- Prior art date
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Classifications
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0028—Crystal modifications; Special X-ray patterns of azo compounds
- C09B67/0029—Crystal modifications; Special X-ray patterns of azo compounds of monoazo compounds
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Abstract
MODIFICATIONS OF MIXTURES OF AZO DYESTUFFS STABLE
UNDER DYEING CONDITIONS
Abstract of the disclosure Novel modifications being stable under dyeing conditions of mono-azo-dyestuffs obtained by coupling 1 mole of diazotized 2-cyan-4-nitro-aniline with 1 mole of a mixture of the coupling compo-nents N-n-butyl-N-cyanethyl-aniline (A) and N-ethyl-N-cyanethyl-aniline (B) in a molar ratio of from 50 : 50 to 20 : 80 of A : B, and subsequently treating the formed products each consisting of the dyestuffs of the formulae and
UNDER DYEING CONDITIONS
Abstract of the disclosure Novel modifications being stable under dyeing conditions of mono-azo-dyestuffs obtained by coupling 1 mole of diazotized 2-cyan-4-nitro-aniline with 1 mole of a mixture of the coupling compo-nents N-n-butyl-N-cyanethyl-aniline (A) and N-ethyl-N-cyanethyl-aniline (B) in a molar ratio of from 50 : 50 to 20 : 80 of A : B, and subsequently treating the formed products each consisting of the dyestuffs of the formulae and
Description
The present invention relates to novel modifications being stable under dyeing conditions of monoazo-dyestuffs obtained by coupling 1 mole of diazotized 2-cyan-4-nitro-aniline with 1 mole of a mixture of the coupling components N-n-butyl-N-cyanethyl-anil-ine (A) and N-ethyl-N-cyanethyl-aniline (B) in a molar ratio of from 50:50 to 20:80 of A:B, and subsequently treating the formed products each consisting of the dye~stuffs of the formulae CN
02N ~N=N ~;3 CH2 CH2 C
and CN
02 ~ N=N ~ N \ C2~5 a) by heating in an aqueous suspension to a temperature between 90 and 150C, or b) by heating in an organic solvent to a temperature be-tween 90 and 150C, or c) by grinding at a temperature between 90 and 100C, or d) by drying from aqueous-moist state at a temperature between 100 and 120C.
Upon coupling 1.0 mole of diazotized 2-cyano-4-nitro-aniline with a mixture of 0.5 mole (A) and 0.5 mole (B) without any specific final treatment, a mixture component dyestuff is obtained being present as the ~-modification which is unstable under dyeing conditions and which has the X-ray diffraction diagram shown in figure 1 with the characteristic reflexes at the following glance angles ~(Cu-K~-irradiation) and at the indicated degrees ~ - 2 -Qll of intensity:
Figure 1:
[~] 2.55 2.85 5.45 6.65 7.1 8.213.513.55 relative 76 100 76 70 60 67 93 83 Intensity Due to the specific final treatments described below, there is formed the ~-modification ~hich is stable under the dyeing conditions and which has the X-ray diffraction diagram of figure
02N ~N=N ~;3 CH2 CH2 C
and CN
02 ~ N=N ~ N \ C2~5 a) by heating in an aqueous suspension to a temperature between 90 and 150C, or b) by heating in an organic solvent to a temperature be-tween 90 and 150C, or c) by grinding at a temperature between 90 and 100C, or d) by drying from aqueous-moist state at a temperature between 100 and 120C.
Upon coupling 1.0 mole of diazotized 2-cyano-4-nitro-aniline with a mixture of 0.5 mole (A) and 0.5 mole (B) without any specific final treatment, a mixture component dyestuff is obtained being present as the ~-modification which is unstable under dyeing conditions and which has the X-ray diffraction diagram shown in figure 1 with the characteristic reflexes at the following glance angles ~(Cu-K~-irradiation) and at the indicated degrees ~ - 2 -Qll of intensity:
Figure 1:
[~] 2.55 2.85 5.45 6.65 7.1 8.213.513.55 relative 76 100 76 70 60 67 93 83 Intensity Due to the specific final treatments described below, there is formed the ~-modification ~hich is stable under the dyeing conditions and which has the X-ray diffraction diagram of figure
2 with the characteristic reflexes at the aforespecified glance angles ~(Cu-K-irradiation) with the indicated degrees of intensity:
~ - 2a -~' , HOE 76/F 232 Figure 2:
-[e~ 4.85 7.5 9.65 11.5 13.0 13.5 13.95 relativ~ 100 90 34 77 30 32 27 Intensity When coupling 1.0 mole of dia`zotized 2-cyano-4-nitro-aniline with a mixture of 0.2 mole (A) and 0.8 mole (B) there are ob-ta.ined, under normal conditions, i.e. without any subsequent specific final treatment, mixtures of azo dyestuffs being presen-.
as the ~-modification which is unstable under dyeing conditions and which shows the X-ray diffraction diagram of figure 3 with the characteristic reflexes at the following glance angles e (Cu-K ~-irradiation) and at the indicated degrees of intensity:
Figure 3:
[e] 2.3 6.4 6.8 10.2 ii.8 13.~5 relative 60 60 75 '51 36 100 Intensity The ~-modificatlon which is unstable under dyeing oondi.tions may be converted to the J-modification which is stable unde..
dyeing conditions and which has the X-ray diffraction diagram shown in figure 4 with the characteristic reflexes at the i,ndi-cated glance angles e (Cu-Ko~-irradiation) with the specified degrees of intensity, by means of the below described spec fic final treatments.
Figure 4:
[~ '5.1 8.2 10.2 11.45 12.15 14.7 relative 100 49 34 43 67 29 Intensity ~ 3 _ Q~l HOE 76/F 23~
If diazoti2ed 2-cyano-4-nitro-aniline is coupled with mix-tures of the two azo components (A) and (B), the molar ratios of which range from 50 : 50 to 20 : 80 of (A) : (B), there are alsc obtained mixtures of azo dyestuffs with crystallographic mixed S phases which may yield modifications also stable under dyeing conditions, due to suitable final ~reatments such as they are des-cribed hereafter, and which modifications show similar interesting properties for industrial application purposes ].ike the dyestuffs at the mixture ratio of the azo components (A) and (B) of 50 : 50 and 20 : 80.
The below described modifications of samples subjected to final treatment do practically not show any changes of their crystal size and shape under dyeing conditions such as elevated temperature and the presence of dyeing au~iliaries, so that the dyeing properties and the stability of the dispersions, in con-, .
tradistinctlon to the modifications of the dyestuffs not subject-ed to final treatments, are not detrimentally affected. ~en pre-paring the mixtures of azo dyestuffs by coupling diazotized 2-cyano-4-nitro-aniline with a mixture of azo components (A3 a~d (B) it is a convenient processing method to couple always 1 mole of the diazo component with 1 mole of (A) and (B), for otherwise technological problems may be encountered.
The novel modification of the mixtures of azo dyestuffs which are stable under dyeing conditions may be obtair.ed by heating for 1 to 5 hours, optionally under elevated pressure, an aqueous suspension of the unstable modifications, to temperatures of from ~0 to 150 C, preferably from 100 to 120 C.
The novel modifications of the mixture component dyestuffs which are stable under dyeing conditions, may also be obtained by heating the unstable modifications to temperatures of from 90 to 150 C in organic solvents such as alcohols, e.g. butanol, ethers such as dioxane, glycols or glycol ethers.
Furthermore, the novel modifications which are stable under dyeing conditionsmay be obtained by drying the unstable modifi-cations at temperatures of from 100 to 120 DC.
The conversion to the novel~modifications of the mixtures of azo dyestuffs is carried out also by heating the unstable modi-fications in an aqueous suspension, while adding water-soluble organic solvents such as alcohols, butanol, glycols or glycol ethers or dimethylformamide to a temperature range the lower li~it of which is set at 90 C and the upper limit of which isdeten~
by the composition of the mixture of water and organic solvent, but which should not exceed 150 C.
The novel modifications of the mlxtures of azo dyestuffs be-ing stable under dyeing conditions are furthermore obtained by heating an aqueous suspension of the modifications being unstable ` under dyeing conditions, while adding anionio, cationic or non-ionic surface-active compounds at temperatures from 90 to 100 C.
Surface-active compounds suitable for this purpose are, for example, diisobutylnaphthalene sulfonic acid sodium, the addition product of 25 moles of ethylene oxide to 1 mole of stearyl alconol, a mixture of alkyl dimethyl benzyl ammonium chlorides, a fatty acid polyglycol ester or tert. organic phosphoric acid ester of the addition product of 2 moles of ethylene oxide to 1 mole of lauryl alcohol.
Finally, the novel modifications of mixtures of azo dye-stuffs which are stable under dyeing conditions may also be ob-tained by grinding the modifications which are unstable under . , :
- .
,, . :
~lQQli dyeing con~ ons with the addition of customary disp~rsing agents, such ~s alkylated naphthalene sulfonic acids and form-aldehyde or of phenol and formaldehyde, alkali metal salts of lignin sulfonates or sulfite cellulose waste liquor, at tempe-ratures of from 90 to 100 C.
- The modifications of the mixtures of azo dyestuffs which are stable under dyeing conditions are separated, for example, by filtration of the liquid phases and subjected to a known finish-ing process while adding dispersing agents such as al~ylated naphthalene sulfonic acids, polyvinyl sulfonates, condensation products of naphthalene sulfonic acid and formaldehyde, or of phenol and formaldehyde, alkali metal salts of li~nin sulfonates or sulfite cellulose waste liquor, at the usual temperatures which do not exceed 60 C. Customary devices such as ball mills, perl mills or sand mills are suitable for carrying out the fine dis-persion step.
The liquid or pulverulent preparations of the modifications being stable under dyeing conditions are highly suitable, in contradistinction to comparable preparations of unstable modi-fications, for dyeing any fiber materials made of cellulose esters or synthetic linear polyesters, such as polyethylene gly-col terephthalate, at temperatures of from 100 to 220 C. The stable preparations do not flocculate in an aqueous medium and under the influence of elevated temperatures, a fact which is especially important for dyeing wound-up objects, such as c-oss-wound bobbins, and they give better test results for various dyeing tests.
The parts and percentages méntioned in the following Exampl-111~011 es me~n parts by weight and % by weight, unless otherwise stated.
The following E~amples illustrate the invention:
Example 1 163 parts of 2-cyano-4-nitro aniline are introduced at 5 - 10 ~C
into 700 parts of sulfuric acid (at 95 ~ conc.). At this s~me temperature are then added drop~ise 324 parts of nitrosyl sul-furic aci.d (at 40 ~ conc.) and the whole is stirred for 3 hours at 5 - 10 C. Subse~uently, the thus obtained diazo solution with sulfuric acid is introduced into a mi.xture of ice/water, while stirring viyo~ously.
The dilute diazo solution i5 filtered and charged into an agitation vessel. Tihe solution with hydrochlor~c acid of the mixture being composed of 87 parts of N-et'nyl-~-cyanoethyi-all.,.-line and 101 parts of N-n-butyl-~-cyanoethyl-anilir.e is then added dropwlse into this diazo solution. The dyestuff suspension is diluted to ~our times its volume and agitated overnight at room temperature.
The next morning, the dyestuff is filtered off and washed with water. '~here are obtained 1~00 parts of the moist suction-filtercake correspondin~ to 320 parts of the dry dyestufL. The tllus obtained mixtures of azo dyestuffs has the form of the~_-modification which i.s wlstable ùnder dyeing conditions.
Example 2 A similar dyestuff is obtained, if the process is carried out in analogy to Example 1, but with the use of the solution wi`h hydrochloric acidof amixture of 139 parts of N-ethyl-N-cyano-- ethyl-aniline and 40 parts of N-n-butyl-N-cyanoethyl-aniline aS
~lOQ~
~OE 76/F 232 azo compon~t. There are obtained mixtures of azo dyestuffs ha-ving the form of the ~-modification which are unstable unde- dye_ ing conditions.
Example 3 A similar dyestuff is obtained, if the process is car.ied out in analogy to Example 1, but with the use of the solution with hydrochloric acid of the mi~ture of 104.4 parts o N~ethyl N-cyanoethyl-aniline and 80.8 parts of N-n-butyl-N-cyanoethyl-aniline as azo components. The thus obtained mixtures of azo dyestuffs are unstable.
100 parts of the thus obtained mixtures of azo dyestuffs are refluxed for 2 hours in an aqueous suspension. During this operational step the dyestuff converts to a stable one.
Example 4 100 parts of the mixtures of azo dyestuffs prepared accord-ing to Example 1 are refluxed for 1 hour in an aqueous suspensio~.
During this operational step the unstable ~-modification corver s into the B-modification which is stable under dyeing conditions.
The dyestuff is filtered off and subjected to grinding at rocm temperature with 70 parts of a condensation product consisting c cresol, formaldehyde and sodium bisulfite as dispersing agenl, 80 parts of ethylene glycol and 2 parts of pentachlorophenol-sodium and water, until the dispersion is sufficiently fine.
Example 5 -100 parts of the dyestuff prepared according to Example 2 are agitated for one hour at 95 - 100 ~C in an aqueous suspensioi containing 10 ~ by volume of n-butanol. This operational step converts the unstable ~-mod~fication into the ~-modifica'ion lllO~li HOE 76/F 23~
which is stable under dyeing conditions. The dyestuff is filtered off and then ground as described in Example 4. A liquid dyestuf' preparation with impeccable dyeing properties and sood stability is obtained.
S Example 6 100 parts of the dyestuff prepared according to Example 1 are ground with 100 parts of a ~ondensation product consisting of cresol, formaldehyde, sodium bisulfite and anaphthol sulfonic acid at about 90 C in a perl mill until the dispersion is sufficiently fine, the preparation i5 finally dried in a spraying device after having added further 100 parts of the afore mention-ed condensation product. The thus obtained powder fulfills all requirements of industrial technology.
Example 7 100 parts of the dyestuff prepared in analogy to Example 2 are refluxed for 1 hour in an aqueous suspension containing 0.5 % by volume of the tert. organic phosphoric acid ester of lauryl alcohol with 2 moles or ethylene oxide. There is obtained a dyestuff being stable under dyeing condltions and ha~ing the J-modification.
The dyestuff is filtered-off and ground as described in Examp]e 4. A liquid dyestuff preparation is obtained of impeccable dye-ing properties and good stability.
Example 8 100 parts o the dyestuff prepared according to Example 1 are dried and heated for 1 hour to about 100 C, while stirring, in about 1000 parts of glycol monomethyl ether. There is obtained a dyestuff of B-modification which is stable under dyeing con-ditions. _ g _ The dyest.uff is filtered-off, washed with water and ground as described in ~xample 4. There is obtained a liquid dyestuff pre-paration of impeccable dyeing properties and good stability.
~ - 2a -~' , HOE 76/F 232 Figure 2:
-[e~ 4.85 7.5 9.65 11.5 13.0 13.5 13.95 relativ~ 100 90 34 77 30 32 27 Intensity When coupling 1.0 mole of dia`zotized 2-cyano-4-nitro-aniline with a mixture of 0.2 mole (A) and 0.8 mole (B) there are ob-ta.ined, under normal conditions, i.e. without any subsequent specific final treatment, mixtures of azo dyestuffs being presen-.
as the ~-modification which is unstable under dyeing conditions and which shows the X-ray diffraction diagram of figure 3 with the characteristic reflexes at the following glance angles e (Cu-K ~-irradiation) and at the indicated degrees of intensity:
Figure 3:
[e] 2.3 6.4 6.8 10.2 ii.8 13.~5 relative 60 60 75 '51 36 100 Intensity The ~-modificatlon which is unstable under dyeing oondi.tions may be converted to the J-modification which is stable unde..
dyeing conditions and which has the X-ray diffraction diagram shown in figure 4 with the characteristic reflexes at the i,ndi-cated glance angles e (Cu-Ko~-irradiation) with the specified degrees of intensity, by means of the below described spec fic final treatments.
Figure 4:
[~ '5.1 8.2 10.2 11.45 12.15 14.7 relative 100 49 34 43 67 29 Intensity ~ 3 _ Q~l HOE 76/F 23~
If diazoti2ed 2-cyano-4-nitro-aniline is coupled with mix-tures of the two azo components (A) and (B), the molar ratios of which range from 50 : 50 to 20 : 80 of (A) : (B), there are alsc obtained mixtures of azo dyestuffs with crystallographic mixed S phases which may yield modifications also stable under dyeing conditions, due to suitable final ~reatments such as they are des-cribed hereafter, and which modifications show similar interesting properties for industrial application purposes ].ike the dyestuffs at the mixture ratio of the azo components (A) and (B) of 50 : 50 and 20 : 80.
The below described modifications of samples subjected to final treatment do practically not show any changes of their crystal size and shape under dyeing conditions such as elevated temperature and the presence of dyeing au~iliaries, so that the dyeing properties and the stability of the dispersions, in con-, .
tradistinctlon to the modifications of the dyestuffs not subject-ed to final treatments, are not detrimentally affected. ~en pre-paring the mixtures of azo dyestuffs by coupling diazotized 2-cyano-4-nitro-aniline with a mixture of azo components (A3 a~d (B) it is a convenient processing method to couple always 1 mole of the diazo component with 1 mole of (A) and (B), for otherwise technological problems may be encountered.
The novel modification of the mixtures of azo dyestuffs which are stable under dyeing conditions may be obtair.ed by heating for 1 to 5 hours, optionally under elevated pressure, an aqueous suspension of the unstable modifications, to temperatures of from ~0 to 150 C, preferably from 100 to 120 C.
The novel modifications of the mixture component dyestuffs which are stable under dyeing conditions, may also be obtained by heating the unstable modifications to temperatures of from 90 to 150 C in organic solvents such as alcohols, e.g. butanol, ethers such as dioxane, glycols or glycol ethers.
Furthermore, the novel modifications which are stable under dyeing conditionsmay be obtained by drying the unstable modifi-cations at temperatures of from 100 to 120 DC.
The conversion to the novel~modifications of the mixtures of azo dyestuffs is carried out also by heating the unstable modi-fications in an aqueous suspension, while adding water-soluble organic solvents such as alcohols, butanol, glycols or glycol ethers or dimethylformamide to a temperature range the lower li~it of which is set at 90 C and the upper limit of which isdeten~
by the composition of the mixture of water and organic solvent, but which should not exceed 150 C.
The novel modifications of the mlxtures of azo dyestuffs be-ing stable under dyeing conditions are furthermore obtained by heating an aqueous suspension of the modifications being unstable ` under dyeing conditions, while adding anionio, cationic or non-ionic surface-active compounds at temperatures from 90 to 100 C.
Surface-active compounds suitable for this purpose are, for example, diisobutylnaphthalene sulfonic acid sodium, the addition product of 25 moles of ethylene oxide to 1 mole of stearyl alconol, a mixture of alkyl dimethyl benzyl ammonium chlorides, a fatty acid polyglycol ester or tert. organic phosphoric acid ester of the addition product of 2 moles of ethylene oxide to 1 mole of lauryl alcohol.
Finally, the novel modifications of mixtures of azo dye-stuffs which are stable under dyeing conditions may also be ob-tained by grinding the modifications which are unstable under . , :
- .
,, . :
~lQQli dyeing con~ ons with the addition of customary disp~rsing agents, such ~s alkylated naphthalene sulfonic acids and form-aldehyde or of phenol and formaldehyde, alkali metal salts of lignin sulfonates or sulfite cellulose waste liquor, at tempe-ratures of from 90 to 100 C.
- The modifications of the mixtures of azo dyestuffs which are stable under dyeing conditions are separated, for example, by filtration of the liquid phases and subjected to a known finish-ing process while adding dispersing agents such as al~ylated naphthalene sulfonic acids, polyvinyl sulfonates, condensation products of naphthalene sulfonic acid and formaldehyde, or of phenol and formaldehyde, alkali metal salts of li~nin sulfonates or sulfite cellulose waste liquor, at the usual temperatures which do not exceed 60 C. Customary devices such as ball mills, perl mills or sand mills are suitable for carrying out the fine dis-persion step.
The liquid or pulverulent preparations of the modifications being stable under dyeing conditions are highly suitable, in contradistinction to comparable preparations of unstable modi-fications, for dyeing any fiber materials made of cellulose esters or synthetic linear polyesters, such as polyethylene gly-col terephthalate, at temperatures of from 100 to 220 C. The stable preparations do not flocculate in an aqueous medium and under the influence of elevated temperatures, a fact which is especially important for dyeing wound-up objects, such as c-oss-wound bobbins, and they give better test results for various dyeing tests.
The parts and percentages méntioned in the following Exampl-111~011 es me~n parts by weight and % by weight, unless otherwise stated.
The following E~amples illustrate the invention:
Example 1 163 parts of 2-cyano-4-nitro aniline are introduced at 5 - 10 ~C
into 700 parts of sulfuric acid (at 95 ~ conc.). At this s~me temperature are then added drop~ise 324 parts of nitrosyl sul-furic aci.d (at 40 ~ conc.) and the whole is stirred for 3 hours at 5 - 10 C. Subse~uently, the thus obtained diazo solution with sulfuric acid is introduced into a mi.xture of ice/water, while stirring viyo~ously.
The dilute diazo solution i5 filtered and charged into an agitation vessel. Tihe solution with hydrochlor~c acid of the mixture being composed of 87 parts of N-et'nyl-~-cyanoethyi-all.,.-line and 101 parts of N-n-butyl-~-cyanoethyl-anilir.e is then added dropwlse into this diazo solution. The dyestuff suspension is diluted to ~our times its volume and agitated overnight at room temperature.
The next morning, the dyestuff is filtered off and washed with water. '~here are obtained 1~00 parts of the moist suction-filtercake correspondin~ to 320 parts of the dry dyestufL. The tllus obtained mixtures of azo dyestuffs has the form of the~_-modification which i.s wlstable ùnder dyeing conditions.
Example 2 A similar dyestuff is obtained, if the process is carried out in analogy to Example 1, but with the use of the solution wi`h hydrochloric acidof amixture of 139 parts of N-ethyl-N-cyano-- ethyl-aniline and 40 parts of N-n-butyl-N-cyanoethyl-aniline aS
~lOQ~
~OE 76/F 232 azo compon~t. There are obtained mixtures of azo dyestuffs ha-ving the form of the ~-modification which are unstable unde- dye_ ing conditions.
Example 3 A similar dyestuff is obtained, if the process is car.ied out in analogy to Example 1, but with the use of the solution with hydrochloric acid of the mi~ture of 104.4 parts o N~ethyl N-cyanoethyl-aniline and 80.8 parts of N-n-butyl-N-cyanoethyl-aniline as azo components. The thus obtained mixtures of azo dyestuffs are unstable.
100 parts of the thus obtained mixtures of azo dyestuffs are refluxed for 2 hours in an aqueous suspension. During this operational step the dyestuff converts to a stable one.
Example 4 100 parts of the mixtures of azo dyestuffs prepared accord-ing to Example 1 are refluxed for 1 hour in an aqueous suspensio~.
During this operational step the unstable ~-modification corver s into the B-modification which is stable under dyeing conditions.
The dyestuff is filtered off and subjected to grinding at rocm temperature with 70 parts of a condensation product consisting c cresol, formaldehyde and sodium bisulfite as dispersing agenl, 80 parts of ethylene glycol and 2 parts of pentachlorophenol-sodium and water, until the dispersion is sufficiently fine.
Example 5 -100 parts of the dyestuff prepared according to Example 2 are agitated for one hour at 95 - 100 ~C in an aqueous suspensioi containing 10 ~ by volume of n-butanol. This operational step converts the unstable ~-mod~fication into the ~-modifica'ion lllO~li HOE 76/F 23~
which is stable under dyeing conditions. The dyestuff is filtered off and then ground as described in Example 4. A liquid dyestuf' preparation with impeccable dyeing properties and sood stability is obtained.
S Example 6 100 parts of the dyestuff prepared according to Example 1 are ground with 100 parts of a ~ondensation product consisting of cresol, formaldehyde, sodium bisulfite and anaphthol sulfonic acid at about 90 C in a perl mill until the dispersion is sufficiently fine, the preparation i5 finally dried in a spraying device after having added further 100 parts of the afore mention-ed condensation product. The thus obtained powder fulfills all requirements of industrial technology.
Example 7 100 parts of the dyestuff prepared in analogy to Example 2 are refluxed for 1 hour in an aqueous suspension containing 0.5 % by volume of the tert. organic phosphoric acid ester of lauryl alcohol with 2 moles or ethylene oxide. There is obtained a dyestuff being stable under dyeing condltions and ha~ing the J-modification.
The dyestuff is filtered-off and ground as described in Examp]e 4. A liquid dyestuff preparation is obtained of impeccable dye-ing properties and good stability.
Example 8 100 parts o the dyestuff prepared according to Example 1 are dried and heated for 1 hour to about 100 C, while stirring, in about 1000 parts of glycol monomethyl ether. There is obtained a dyestuff of B-modification which is stable under dyeing con-ditions. _ g _ The dyest.uff is filtered-off, washed with water and ground as described in ~xample 4. There is obtained a liquid dyestuff pre-paration of impeccable dyeing properties and good stability.
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Novel modifications being stable under dyeing conditions of monoazo-dyestuffs obtained by coupling 1 mole of diazotized 2-cyan-4-nitro-aniline with 1 mole of a mixture of the coupling components N-n-butyl-N-cyanethyl-aniline (A) and N-ethyl-N-cyanethyl-aniline (B) in a molar ratio of from 50 :
50 to 20 : 80 of A : B, and subsequently treating the formed products each consisting of the dyestuffs of the formulae and a) by heating in an aqueous suspension to a temperature between 90 and 150 °C, or b) by heating in an organic solvent to a temperature between 90 and 150 °C, or c) by grinding at a temperature between 90 and 100 °C, or d) by drying from aqueous-moist state at a temperature between 100 and 120 °C.
50 to 20 : 80 of A : B, and subsequently treating the formed products each consisting of the dyestuffs of the formulae and a) by heating in an aqueous suspension to a temperature between 90 and 150 °C, or b) by heating in an organic solvent to a temperature between 90 and 150 °C, or c) by grinding at a temperature between 90 and 100 °C, or d) by drying from aqueous-moist state at a temperature between 100 and 120 °C.
2, The novel modification .beta. being stable under dyeing conditions of the monoazo-dyestuff obtained by coupling 1 mole of diazotized 2-cyan-4-nitro-aniline with 1 mole of a mixture of the coupling components N-n-butyl-N-cyanethyl-aniline and N-ethyl-N-cyanethyl-aniline in a molar ratio of 50 : 50, said novel modification .beta. being characterized by an X-ray diffraction pattern with characteristic reflexes at the following glance angles .theta. (Cu-K .alpha.-radiation) with the relative intensities as given below:
[.theta.] 4.85 7.5 9.65 11.5 13.0 13.5 13.95 relative 100 90 34 77 30 32 25 Intensity
[.theta.] 4.85 7.5 9.65 11.5 13.0 13.5 13.95 relative 100 90 34 77 30 32 25 Intensity
3. The novel modification .delta. being stable under dyeing conditions of the monoazo-dyestuff obtained by coupling 1 mole of diazotized 2-cyan-4-nitro-aniline with 1 mole of a mixture of the coupling components N-n-butyl-N-cyanethyl-aniline (A) and N-ethyl-N-cyanethyl-aniline (B) in a molar ratio of 20 : 80 of A : B, said novel modification .delta. being characterized by an X-ray diffraction pattern with characteristic reflexes at the following glance angles .theta. (Cu-K .alpha.-radiation) with the relative intensities as given below:
[.theta.] 5.1 8.2 10.2 11.45 12.15 14.7 relative 100 49 34 43 67 29 Intensity
[.theta.] 5.1 8.2 10.2 11.45 12.15 14.7 relative 100 49 34 43 67 29 Intensity
4. Process for the manufacture of novel modifications being stable under dyeing conditions of monoazo-dyestuffs obtained by coupling diazotized 2-cyan-4-nitro-aniline with a mixture of the coupling components N-n-butyl-N-cyanethyl-aniline (A) and N-ethyl-N-cyanethyl-aniline (B), wherein 1 mole of diazotized 2-cyan-4-nitro-aniline is coupled with 1 mole of a mixture of the said two coupling components in a molar ratio of from 50 : 50 to 20 : 80 of A : B, and the formed products of the formulae and are a) heated in an aqueous suspension of a temperature between 90 and 150 °C, or b) heated in an organic solvent at a temperature between 90 and 150 °C, or c) ground in the presence of a dispersing agent at a temperature between 90 and 100 °C, or d) is dried from aqueous-moist state at a temperature between 100 and 120 °C.
5. The process as claimed in claim 4a, wherein the heating is performed after the additon of a water-soluble organic solvent.
6. The process as claimed in claim 4a, wherein the heating is performed after the addition of an anionic, cationic or non-ionic surface-active agent.
7. A process as claimed in anyone of claims 4 to 6, wherein 1 mole of diazotized 2-cyan-4-nitro-aniline is coupled with a mixture of the coupling components A and B in a molar ratio of 50 : 50, and the formed product is treated as there described obtaining the novel modification .beta. being stable under dyeing conditions and being characterized by an X-ray diffraction pattern with characteristic reflexes at the following glance angles .theta. (Cu-K
.alpha.-radiation) with the relative intensities as given below:
[.theta.] 4.85 7.5 9.65 11.5 13.0 13.5 13.95 relative 100 90 34 77 30 32 25 Intensity
.alpha.-radiation) with the relative intensities as given below:
[.theta.] 4.85 7.5 9.65 11.5 13.0 13.5 13.95 relative 100 90 34 77 30 32 25 Intensity
8. A process as claimed in anyone of claims 4 to 6, wherein 1 mole of diazotized 2-cyan-4-nitro-aniline is coupled with a mixture of the coupling components A and B in a molar ratio of 20 : 80 of A : B, and the formed product of the two monoazo-dyestuffs is treated as there described obtaining the novel modification .delta. being stable under dyeing conditions being character-ized by an X-ray diffraction pattern with characteristic reflexes at the following glance angles .theta. (Cu-K .alpha.-radiation) with relative intensities as given below:
[.theta.] 5.1 8.2 10.2 11.45 12.15 14.7 relative 100 49 34 43 67 29 Intensity
[.theta.] 5.1 8.2 10.2 11.45 12.15 14.7 relative 100 49 34 43 67 29 Intensity
9. A process for the dyeing of a textile material consisting of or containing cellulosic ester or synthetic linear polyester fibers at a temperature between 100 and 220°C, wherein an aqueous dispersion of a novel modifica-tion as claimed in claim 1 is used.
10. A process for the dyeing of a textile material consisting of or containing cellulosic ester or synthetic linear polyester fibers at a temperature between 100 and 220°C, wherein an aqueous dispersion of a novel modification as claimed in claim 2 is used.
11. A process for the dyeing of a textile material consisting of or containing cellulosic ester or synthetic linear polyester fibers at a temperature between 100 and 220°C, wherein an aqueous dispersion of a novel modification as claimed in claim 3 is used.
12. A textile material consisting of or containing cellulosic ester or synthetic linear polyester fibers, whenever dyed or printed by a process as claimed in claim 9, 10 or 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2642730.5 | 1976-09-23 | ||
| DE762642730A DE2642730C3 (en) | 1976-09-23 | 1976-09-23 | Color-stable modification of mixed dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1110011A true CA1110011A (en) | 1981-10-06 |
Family
ID=5988600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA287,268A Expired CA1110011A (en) | 1976-09-23 | 1977-09-22 | Modifications of mixtures of azo dyestuffs stable under dyeing conditions |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS6047310B2 (en) |
| BE (1) | BE859004A (en) |
| BR (1) | BR7706341A (en) |
| CA (1) | CA1110011A (en) |
| CH (1) | CH645496GA3 (en) |
| DE (1) | DE2642730C3 (en) |
| FR (1) | FR2365612A1 (en) |
| GB (1) | GB1542751A (en) |
| IN (1) | IN146933B (en) |
| IT (1) | IT1085046B (en) |
| MX (1) | MX4570E (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58225156A (en) * | 1982-06-21 | 1983-12-27 | Gosei Senriyou Gijutsu Kenkyu Kumiai | Monoazo dye and preparation thereof |
| JPS62120628U (en) * | 1986-01-24 | 1987-07-31 | ||
| JPS63126306A (en) * | 1986-11-17 | 1988-05-30 | Hitachi Ltd | Negative feedback amplifier circuit |
| CN105623299B (en) * | 2015-11-19 | 2018-03-23 | 浙江闰土研究院有限公司 | A kind of compound novel crystal forms, preparation method and the usage |
-
1976
- 1976-09-23 DE DE762642730A patent/DE2642730C3/en not_active Expired
-
1977
- 1977-09-15 IN IN1408/CAL/77A patent/IN146933B/en unknown
- 1977-09-20 CH CH1148777A patent/CH645496GA3/en unknown
- 1977-09-21 IT IT2782377A patent/IT1085046B/en active
- 1977-09-22 MX MX77307U patent/MX4570E/en unknown
- 1977-09-22 JP JP52113417A patent/JPS6047310B2/en not_active Expired
- 1977-09-22 CA CA287,268A patent/CA1110011A/en not_active Expired
- 1977-09-22 BR BR7706341A patent/BR7706341A/en unknown
- 1977-09-23 GB GB7739759A patent/GB1542751A/en not_active Expired
- 1977-09-23 BE BE181161A patent/BE859004A/en not_active IP Right Cessation
- 1977-09-23 FR FR7728699A patent/FR2365612A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| MX4570E (en) | 1982-06-17 |
| CH645496GA3 (en) | 1984-10-15 |
| GB1542751A (en) | 1979-03-21 |
| DE2642730B2 (en) | 1978-07-20 |
| DE2642730C3 (en) | 1979-03-08 |
| JPS6047310B2 (en) | 1985-10-21 |
| DE2642730A1 (en) | 1978-03-30 |
| BE859004A (en) | 1978-03-23 |
| JPS5340019A (en) | 1978-04-12 |
| BR7706341A (en) | 1978-06-06 |
| FR2365612A1 (en) | 1978-04-21 |
| IN146933B (en) | 1979-10-20 |
| IT1085046B (en) | 1985-05-28 |
| FR2365612B1 (en) | 1982-11-12 |
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