MXPA01003120A - Disperse dye mixtures - Google Patents

Disperse dye mixtures

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Publication number
MXPA01003120A
MXPA01003120A MXPA/A/2001/003120A MXPA01003120A MXPA01003120A MX PA01003120 A MXPA01003120 A MX PA01003120A MX PA01003120 A MXPA01003120 A MX PA01003120A MX PA01003120 A MXPA01003120 A MX PA01003120A
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MX
Mexico
Prior art keywords
pigment
mixture
formula
pigments
component
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MXPA/A/2001/003120A
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Spanish (es)
Inventor
David Brierley
Alan Leaver
James Franklin Bullock
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Basf Aktiengesellschaft
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Publication of MXPA01003120A publication Critical patent/MXPA01003120A/en

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Abstract

A dye mixture comprises:a) at least one pyrroline type dye of formula (I), wherein R1 is H, C1-20alkyl or C2-20alkenyl;and D is aryl;and b) at least one anthraquinone type dye of formula (II), wherein RB is (CH2) nORB1;RB1 is C1-6alkyl or C1-6alkoxy-C1-6alkyl;n is 1-6;and ZB is O or NH.

Description

DISPERSED PIGMENT MIXES Description of the invention This invention relates to mixtures of dispersed pigments or dyes, to compositions comprising the dispersions of such mixtures and to processes for coloring synthetic materials with such mixtures. More particularly, the invention relates to mixtures of pigments of the so-called pyrroline type with agueilles of the so-called anthraguinone type. Pigments of the pyrroline type are described, for example, in US-A-3013013, US-A-3013018, GB-A-2191498, EP-A-0327077, EP-A-0511625 and WO-A-94010248. In particular, document O-A-94010248 discloses pigments of the pyrroline type having the formula (1) Fórmu-La_ C1) where D is a group of the formula (2) Formula (2 or a group of the formula (3) Formula (3) or a group of the formula (4) Formula 4 R1 is alkenyl, cycloalkyl, aryl, alkenyl or aralguilo, each of which may be optionally substituted; R2 is optionally substituted alkyl of 7 to 20 carbon atoms; or R1 and R2 together with the nitrogen atom to which they are attached form a pyrrolidino or piperidino ring; R3 is alkenyl, alkenyl, or aralguilo, each of which may be optionally substituted, -S02-alkyl, -S02-aryl, or -COR in which R is -H or alkenyl, phenyl, cycloalkyl or aralguilo, each of which may be optionally substituted, or -H; and R4 is a group that removes erons; R6 is alkyl of 1 to 16 carbon atoms optionally substituted; or R1 and R6 conjunctly with the nitrogen atom to which they are attached form a pyrrolidino or piperidino ring; R7, R8, R9 and R10 are each independently alkyl, cycloalguyl, aryl, alkenyl or aralguilo, each of which may be optionally substituted or -H; it is oxygen or sulfur; Z is a direct bond or N-R11 in which R11 is -H or optionally substituted alkyl or aryl; Ring A is unsubstituted apart from the group -NR1R2 or is substituted by 1 to 4 additional groups; and Ring B is, not substituted or substituted with 1 to 3 groups; except for 3- (4- (N, N-di-n-octyl) phenyl) -4-cLano-5-dici.anomethylidene-2-oxo-2,5-dihydropyrrole with the proviso that: (a) when D is a group of the formula (3), R1 and R6 are different and R1 is not -C2H5, -C3H7 or -C4H9 when R6 is -C2H4phenyl, -C3H6phenyl and ethyl substituted with -OH, -CN, -OCH3, -OC2H4OC2H5, -NHCOCHs-O-phenyl and -NHS02CH3; or (b) at least one of R1 and R6 is branched chain alkyl. Commercially available pigments of the pyrroline type are, for example, pigments of the formula: where RA is hydrogen (Brilliant Blue F2B-S Kayalon polyester); or CH2CH = CH2 (Blue-Green polyester FG-S from Kayalon); and pigments of the formula where XA is C4E9 a? A is C_H. (CH3) C_Hn. The pigments of the anthraquinone type are also well known. For example, the pigments and pigment mixtures each within the formula given below are commercially available as Disperse Blue 60 pigments of C.l. : where RB is (CH2)? -O-RB1, in which n is 1-6 and RB1 is a linear or branched alkyl or alkoxy (and the examples of RB are -C2H40CH3, C3H60CH3 / C3H60C2H5 and C3H60C20CH3) and ZB is oxygen or NH. However,. If the pigments of the pyrroline type alone (or mixtures of such pyrroline-type pigments) are pigmented on polyester, the constitution until very deep shadows is difficult to achieve, the firmness of light is the best of the average cases, the pigments tend to be more very sensitive to changes in the pH of the pigmentation and undesirable reddish shadows are sometimes observed. If the pigments of the anthraquinone type alone (or mixtures of such anthraguinone-like pigments) are colored on polyester ,. these often show very good light firmness, but with poor increase. In addition, these are dyeing very weak and therefore expensive to color the polyester. In addition, liguid or high-strength grain formulations can not be achieved. In addition, if the good increase can be achieved, the shadow becomes more opaque as the pigment accumulates.
It has now surprisingly been found that if certain pigments of the pyrroline type are mixed with certain pigments of the anthraquinone type, more brilliant shadows are maintained as the pigments accumulate. In addition, pigmentations have good light firmness. In particular, when compared to anthraquinone pigments alone, when mixtures of pyrroline pigments are used, the products of high color strength can be easily formulated, with greater cost effectiveness. Thus, the invention provides a mixture of pigments comprising: (A) at least one pyrroline pigment of the formula (i); (i: wherein R 1 is hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 2 to 20 carbon atoms, and D is aryl, and (B) at least one pigment of the anthraguinone type of the formula (II); (II wherein RB is (CH? AORB1; RB1 is a group (C 1-6 alkoxy) - (C 1-6 -alkyl) or straight-chain or branched C 1-6 -alkyl; is 1-6, and ZB is O or NH The component (A) preferably comprises a pigment of the formula (I) wherein D is a group of the Formula (a) (a) wherein each of R2 and R3 is independently an alkyl, cycloalguyl, aryl, alkenyl or aralkyl group. In the above formula (I), the alkyl group represented by any of R1-R3 is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 12 carbon atoms and especially an alkyl group of 1. to 8 carbon atoms. The cycloalkyl group represented by R2 or R3 is preferably a cycloalkyl group of 4 to 8 carbon atoms and more preferably a cyclohexyl group. The aryl group represented by R2 or R3 is preferably phenyl. The alkenyl group represented by any one of R1-R3 is preferably an alkenyl of 2 to 10 carbon atoms, more preferably an alkenyl of 2 to 6 carbon atoms and especially an alkenyl group of 2 to 3 carbon atoms, such as allyl. The aralkyl group represented by any of R1-R3 is preferably a phenyl-alkyl group of 1 to 6 carbon atoms, more preferably a phenyl-alkenyl group of 1 to 3 carbon atoms, especially phenylethyl or 3-phenylpropyl. The alkyl group represented by R 3 is more preferably an alkyl group of 7 to 15 carbon atoms, still more preferably an alkyl group of 7 to 12 carbon atoms and especially an alkyl group of 7 to 9 carbon atoms. The alkyl group represented by R 1 is more preferably an alkyl group of 1 to 6 carbon atoms and still more preferably an alkyl group of 1 to 4 carbon atoms. R1 is special and preferably -H, alkyl of 1 to 4 carbon atoms or alkenyl of 2 to 3 carbon atoms, more preferably -H or alkyl of 1 to 4 carbon atoms and especially -H. D is preferably a group of Formula (a). The alkyl groups represented by any one of R1 to R3 can be straight or branched chain alkyl groups. R 2 is preferably alkyl of 1 to 12 carbon atoms, more preferably alkenyl of 1 to 8 carbon atoms, especially alkenyl of 1 to 8 unsubstituted carbon atoms. R3 can be albuyl of 7 to 12 carbon atoms and preferably alkyl of 7 to 9 carbon atoms, especially alkyl of 7 to 9 unsubstituted carbon atoms or can be alkoyl of 1 to 6 unsubstituted carbon atoms. Where D is a group of Formula (a) it is preferred that one or both of R2 and R3 be branched, more prefrably branched at the a or β position, for example 1- or 2-. It is preferred that R2 and R3 be different. It is also preferred that ring A is unsubstituted apart from the group NR2R3. A preferred subgroup of pigments of the formula (I) is that in which D is a group of the Formula (a): R1 is alguyl or -H; R2 is alguilo; R3 is albuils of 7 to 20 carbon atoms; and Ring A is unsubstituted apart from the -NR2R3 group. Another preferred subgroup of pigments of the formula (I) is that in which D is a group of the Formula (a); R1 is -H or alguilo; R 2 is unsubstituted alkyl of 1 to 8 carbon atoms; R3 is unsubstituted alkyl of 1 to 6 carbon atoms; and Ring A is unsubstituted apart from the group -NR2R3; and R2 and R3 are different or at least one of R2 and R3 is a branched chain alkenyl. An especially preferred subgroup of pigments of the formula (I) is that in which D is a group of the Formula (a): R1 is -H; R 2 is alkenyl of 1 to 8 unsubstituted carbon atoms; R3 is unsubstituted alkyl of 7 to 9 carbon atoms; and Ring A is unsubstituted apart from the -NR2R3 group. A further especially preferred subgroup of the pigments of the formula (I) is that in which D is a group of the Formula (a); R1 is -H; R2 is n-propyl or n-butyl; R3 is 1-methylhexyl or 2-ethylhexyl; and Ring A is unsubstituted apart from the -NR2R3 group.
The typical preferred CA components in the mixtures exemplifying the invention are: (1) a pyrroline pigment of the formula (I), wherein R 1 is hydrogen, R 2 is C 4 H 9 and R 3 is 1-methyl-n-hexyl ( A1) or a mixture thereof with up to 10% by weight of the component (A), of a pyrroline pigment (A2) of the formula (I) ', wherein R1 is hydrogen and each of R2 and R3 is C4H9; (2) a pyrroline pigment of the formula (I), where R1 is hydrogen, R2 is ethyl and R3 is n-octyl (A3) or 2-ethyl-n-hexyl (A4) or a mixture of pigments (A3) and (A4); and (3) a pyrroline-type pigment of the formula (I), wherein R2 is C4H9, R3 is 3-phenylpropyl and R1 is hydrogen (A5) or allyl (A6) or a mixture of pigments (A5) and (A6) . When R1 is hydrogen, the pigments of the formula (I) may exist in a tautomeric form represented by the formula (IA); Formula (IA) where: D is as defined above in the present. The pigments of the formula (I) wherein D is a group of the formula (a) can be prepared by the reaction of an aniline of the formula (III): Formula (III) wherein the ring A is as defined above, firstly with a compound of the formula R2X in which R2 is as defined above and X is a halogen such as -Cl, -Br or -I or another leaving group, such as tosylate, mesylate or alkylsulfonate in the presence of a base such as an alkali metal carbonate or alkaline earth metal carbonate such as potassium carbonate or calcium carbonate, and secondly with a compound of the formula, R3X in which R3 and X are as defined above in the presence of a base as defined above to form an aromatic amine of the formula (IV): Formula (IV) r Alternatively, the aromatic amine of the formula (IV) can be prepared by the reductive alkylation of the aniline of the formula (III) with an appropriate ketone or aldehyde. The reductive alkylation may be carried out in an inert liquid medium such as an alcohol or ester optionally in the presence of an acid such as an aliphatic carboxylic acid, eg eg acetic and propionic acids and aromatic sulfonic acid for example. 4-toluenesulfonic acid using a metal or a supported metal catalyst such as palladium or platinum on carbon and hydrogen, and optionally at elevated temperature and pressure. Alternatively, reducing agents such as sodium borohydride can also be used. After the reductive alkylation a second algal group can be introduced as described above. The aromatic amine of the formula (IV) is then reacted with a 3-halopyrrole of the formula (V): Fórn - (V) wherein R1 is as defined above and X is preferably a halogen such as -Cl or -Br to form a compound of the formula (I). The reaction may be carried out in a liquid medium such as N, N-di-ethyl formamide, N, N-di-a-J -acetamide, sulfoxide, dimethyl, sulfolane, N-methylpyrrolidone, acetonitrile, toluene or tetrahydrofuran or any mixture thereof. and at a temperature of -20 ° C to 50 ° C. The product can be isolated by any convenient means such as pouring the reaction mixture into a mixture of ice and water and recovering the precipitated product by filtration. The product can be purified by any convenient means such as grinding or recrystallization from organic liquids, particularly alkanols such as methanol, ethanol and esters such as ethyl acetate or mixtures thereof. The 3-halo-3-oxopyrrole of the formula (V) can be prepared by halogenation of a compound which can be represented by the formulas (VI), (VIa) and (VI2) Formula (VI Eó-rmiila. (-V11 Formula (VI ' with a halogenating agent such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride or phosgene at a temperature of -20 ° C to 50 ° C in a liquid medium such as N, N-dimethylformamide, N, N-diethylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, acetonitrile or tetrahydrofuran. The product can be used without isolation with improved performance in the preparation of the compounds of the formula (I) described above or it can be isolated by evaporation of the liquid medium. Alternatively a compound of the formula (IV) can be reacted directly with the compound represented by the formulas (VI), (VI1) or (VI2) in a liquid medium such as toluene in the presence of a halogenating agent such as oxychloride of match. The compounds represented by the formulas (VI) or (VI1) can be prepared by the reaction of the diethyl oxalate with a compound of the formula (VII): Formula (VII) in the presence of a base such as an alkali metal alkoxide, preferably a sodium or potassium alkoxide of 1 to 6 carbon atoms, and especially methoxide, ethoxide, n- or iso-propoxide, n-, iso- or ter- sodium or potassium butoxide, in a medium, preferably an alkanol ,. such as methanol, n- or isopropanol or n-, iso- or tert-butanol, at a temperature of 10 ° C to 60 ° C. The product can be isolated by cooling the reaction mixture and collecting by filtration. The compound of the formula (VII) can be prepared by reacting the malononitrile with a compound of the formula (VIII): NCCH2CN Formula (VIII) in the presence of a base such as sodium methoxide in a liquid medium such as methanol at a temperature of -20 ° C to 60 ° C. The product can be isolated by filtration. A pigment of the formula (I) in which R1 is different from -H can be prepared by reacting the corresponding pigment of the formula (I) in which R1 is -H in a medium, preferably an amide such as dimethylformamide or an ether such as tetrahydrofuran or diethyl ether in the presence of a base, preferably an alkali metal carbonate such as potassium carbonate or an alkali metal hydride such as sodium hydride at a temperature of 0 ° C to 120 ° C with a appropriate aliging agent. Where R1 is alguyl a suitable aliphating agent is an alkenyl halide, preferably an alkyl iodide, alkyl bromide or alkyl chloride. Where R1 is alkenyl, an appropriate alkylating agent is an alkenyl halide, preferably an alkenyl bromide. These pigments can be isolated by evaporation of the medium or by filtration from the reaction mixture. As previously mentioned, the component (A) can be a mixture of two or more pigments of the formula (I) wherein R1 to R3 inclusive, D and the ring A are as defined hereinabove. Reference is now made to component (B), which preferably comprises at least one anthraquinone-type pigment of formula (II), wherein ZB is oxygen or NH, more preferably oxygen, n is 1, 2 or 3, more preferably 2 or 3 and RB1 is methyl, ethyl or methoxyethyl. Thus, it is especially preferred that the component (B) is an anthraguinone pigment of the formula (II) wherein ZB is oxygen and RB is C2H4OCH3, C3H6OCH3, C3H6OC2H5, or C3H6OC2H4OCH3 or a mixture of which two or more such anthraguinone type pigments, especially a mixture of two or three, or pigments (B1), (B2) and (B3), each of the formula (II) in which ZB is oxygen, whose pigment (B1) is a pigment where RB is C3H6OCH3, whose pigment (B2) is a pigment where RB is C3H6OC2OCH3, and whose pigment (B3) is a pigment where RB is C3H6OC2H5; when the component (B) is a mixture of pigments (B1) and (B2), the weight ratio of the dye (B1): dye (B2) is preferably from 30:70 to 60:90 inclusive, more preferably from 45:55 to 48:52. The pigments of the formula (II) wherein RB is hydrogen can be prepared, for example, by reacting 2, 3-dicyano-1,4-diamino-anthraquinone with sulfuric acid. This pigment can then be made to react with a primary amine RBXNH2 to obtain a pigment of the formula (II) wherein RBX is any of the groups of RB other than hydrogen. Alternatively, some such pigments of the formula (II) can be prepared from the 2,3-dicyano-1,4-diaminoanthraguinone by reaction with each of sulfuric acid and a secondary alcohol to provide a pigment where RBX is a secondary alguilo. Yet another method for preparing pigments of the formula (II) wherein RB is a group as previously defined other than hydrogen, is by reaction of the corresponding 1,4-diaminoanthraquinone carboxylic anhydride, with a primary amine RBXNH2 where RBX is as defined previously. Such reactions are described in Vent ataraman, The Chemistry of Synthetic Dyes, Academic Press, New York and London, 1970, Vol. III, pages 413-415. In general, in a preferred mixture of components (A) and (B), the weight ratio of component (A): component (B) is from 3:97 to 60:40 inclusive, more preferably from 8:92 to 40. : 60 inclusive, especially from 10:90 to 30:70 inclusive. In especially preferred mixtures of the components (A) and (B), the component (A) is: (1) a pyrroline-type pigment of the formula (I), wherein R1 is hydrogen, R2 is C4H9 and R3 is 1- methyl-n-hexyl (A1) or a mixture thereof with up to 10% by weight of the component (A), or a pyrroline-type pigment (A2) of the formula (I), wherein R1 is hydrogen and each R2 and R3 is C4H9; or (2) a pyrroline pigment of the formula (I), wherein R 1 is hydrogen, R 2 is ethyl and R 3 is n-octyl (A3) or 2-ethi.La-he i 1 (A4) or a mixture of the pigments (A3) and (A4); or (3) a pyrroline-type pigment of the formula (I), wherein R2 is C4H9, R3 is 3-phenylpropyl and R1 is hydrogen (A5) or allyl (A6) or a mixture of pigments (A5) and (A6); and component (B) is a mixture of pigments (B1) and (B2) anthracguin type, each of the formula (II), whose pigment (B1) is a pigment where ZB is oxygen and RB is C3H6OCH3 and whose pigment (B2) is a pigment where ZB is oxygen and RB is C3H6OCH2CH2OCH3, wherein the weight ratio of the pigment (B1): pigment (B2) is preferably from 45.55 to 48:52. At least for a mixture of component A (1), with component (B), the proportion by weight of component A (1): component (B) is preferably from 5:90 to 30:70 inclusive. A mixture exemplifying the invention of at least one pigment of the formula (I) component (A) and at least one pigment of the formula (II) component (B) may additionally comprise at least one other pigment (component C), especially a yellow, orange, red or brown pigment capable of producing a marine or black shade.
Mixtures exemplifying the invention can be prepared by a number of methods including (1) Co-crystallization Typically, the pigments are dissolved in a hot solvent, for example, by placing the pigments in a suitable solvent and heating to the reflux temperature of the solvent until the pigments are dissolved, after which it is filtered to provide a solution , then the solution is allowed to cool and the crystals are formed. The resulting mixture can then undergo additional processing, such as milling and spray drying. Examples of suitable solvents for this process are organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbon hydrocarbons. alicyclics, alcohols, amides, sulfoxides, esters, ketones and ethers. Specific examples of organic solvents are toluene, ethyl cellosolve, acetone, chlorobenzene, pyridine, dimethylformamide, dimethyl sulfoxide, ethyl acetate, benzene, tetrahydrofuran and cyclohexane. (2) Co-grinding (a) The pigments are mixed and then ground together to give an intimate mixture that is then spray dried to give a solid mixture; or (b) each pigment is ground separately and then mixed in the prescribed proportion before spray drying. (3) Anhydrous mixture Each pigment is spray-dried separately and then mixed in the required ratio by a dry mixing process. The mixtures give especially bright shadows which are kept as the pigments accumulate. _ The pigmentations with the mixtures have good light firmness. The blends have high color strength and can be formulated easily and at low cost. Mixtures which exemplify the invention provide especially useful dispersed pigments, valuable for the coloring of synthetic textiles and fiber blends thereof, by exhaust pigment, calender-dyeing or printing, and can be formed into dispersions for this purpose. . These can also be used, for example, in ink jet printing of textile and non-textile materials, pigment diffusion, thermal transfer printing and in the coloring of plastics. According to other aspects, the invention provides a composition comprising at least the mixture of pigment and a dispersing agent, surfactant or wetting agent, suitable for providing with such dispersion and also a process for coloring a synthetic textile or a mixture of fibers of the same which comprises the application to the synthetic textile or fiber mixture of a mixture comprising at least one pigment of the formula (I) and at least one pigment of the formula (II). The synthetic textile material can be selected from aromatic polyester, especially polyethylene terephthalate, polyamide, especially polyhexamethylene adipamide, secondary cellulose acetate, cellulose triacetate and natural textile materials, especially cellulosic materials and wool. An especially preferred textile material is an aromatic polyester or blend of fibers thereof, with fibers of any of the textile materials previously mentioned. Especially preferred fiber blends include polyester-cellulose aglets, such as polyester-cotton, and polyester-wool. The textile materials or mixtures thereof may be in the form of filaments, loose fibers, yarn or woven or knitted fabrics. Mixtures of pigments of formulas (I) and (II) optionally in conjunction with other dispersed pigments can be applied to synthetic textiles or blends of fibers by processes that are conventionally employed in the application of dispersed pigments to such materials and mixtures of fibers. Suitable process conditions can be selected from the following: (i) exhaust pigmentation at a pH of 4 to 6.5, at a temperature of 125 ° C to 140 ° C for 10 to 120 minutes under a pressure of 1 to 2 bar, optionally adding a hijacker; (ii) continuous pigmentation at a pH of 4 to 6.5, at a temperature of 190 ° C to 225 ° C for 15 seconds to 5 minutes, with an optional migration inhibitor being added; (iii) direct printing at a pH of 4 to 6.5, at a temperature of 160 ° C to 185 ° C for 4 to 15 minutes for steam stream at high temperature, at a temperature of 19-0 ° C to 225 ° C for 15 seconds to 5 minutes for bake setting with dry heat or at a temperature of 120 ° C to 140 ° C and 1 to 2 bar for 10 to 45 minutes for steam stream under pressure, wetting agents and thickeners (such as alginates) from 5 to 100% by weight of the pigment that is optionally added; (iv) discharge printing (by calendering dyeing by printing on the textile material, drying and overprinting) at a pH of 4 to 6.5, migration inhibitors and thickeners that are optionally added; (v) pigmentation per carrier at a pH of 4 to 6.5, at a temperature of 95 ° C to 100 ° C using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol, being optionally added sequestrants; and (vi) atmospheric pigmentation of acetate, triacetate and nylon at a pH of 4 to 6.5, at a temperature of 85 ° C for acetate or at a temperature of 90 ° C for triacetate and nylon for 15 to 90 minutes, optionally added hijackers. In all the above processes, the pigment mixture can be applied as a dispersion comprising from 0.001% to 6%, preferably from 0.005 to 4%, of the mixture of pigments in an aqueous medium. A particular aspect of the invention provides a composition comprising a mixture of pigments (I) and (II), optionally at least one other dispersed pigment and, optionally, at least one additional ingredient conventionally used in coloring applications such as an agent dispersant, surfactant or a wetting agent. The composition typically comprises from 1 to 65%, preferably from 10 to 60%, more preferably from 20 to 55%, of the total pigment mixture in a liguid, preferably in an aqueous medium, or solid. The liquid compositions are preferably adjusted to pH 2 to 7, more preferably pH 4 to 6. Typical examples of dispersion agent are lignosulfonates, condensates of naphthalenesulfonic acid / formaldehyde and condensates of phenol / cresol / sulfanilic acid / formaldehyde, typical examples of the wetting agent are alguylaryl ethoxylates which may be sulfonated or phosphated, and typical examples of other ingredients that may be present are inorganic salts, defoamers such as mineral oil or nonanol, organic liquefies, and buffers. The dispersing agents can be present from 10% to 200% on the weight of the pigment mixtures. The wetting agents can be used from 0% to 20% on the weight of the pigment mixtures. The compositions can be prepared by ball milling the pigment mixture with glass spheres or sand in aqueous medium. The compositions may have additions of dispersing agents, fillers and other surfactants, and may be dried by a technique such as spray drying, to give a solid composition comprising from 5% to 6-5%. of the coloring material. In addition to the aforementioned application processes, the pigment mixtures can be applied to synthetic textiles and fiber blends by ink jet printing, the substrates having been optionally pretreated to assist printing. For ink jet applications, the application medium may comprise water and a water-soluble organic solvent, preferably in a weight ratio of 1:99 to 99: 1, more preferably 1:95 to 50:50 and especially in the interval from 10:90 to 40:60. The water-soluble organic solvent preferably comprises an alkanol of 1 to 4 carbon atoms, especially methanol or ethanol, a ketone, especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol, trimethylene glycol, butan -2,3-diol, thiodiglycol or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulfone, especially bis- (2-hydroxyethyl) sulfone or mixtures thereof. The pigment mixtures can also be applied to textile materials using supercritical carbon dioxide, in which case the pigment formulation agents can optionally be omitted. The embodiments of the present invention will now be described in more detail with reference to the following examples, which parts are by weight unless otherwise indicated.
Examples 1-2: Preparation for Individual Pigments Example 1 - Pyrroline Pigment (1) Preparation of 3- (4- (N-butyl-N- (1-methylhexyl) amino) phenyl) -4-cyano-5-dicyanomethylidene-2-oxo-2,5-dihydropyrrole i) A mixture of 100 parts of aniline, 220 parts of 2-heptanone, 6 parts of 4-toluenesulfonic acid and 5 parts of palladium on carbon at 3% in a 1-liter autoclave was charged with hydrogen at a pressure of 80 atmospheres and heated to 150 ° C for 40 hours. The cooled reaction mixture was diluted with ethyl acetate, filtered, washed with 1 N hydrochloric acid (6 x 200 parts) and water (2 x 200 parts), the ethyl acetate was separated and dried over sodium sulfate. magnesium before evaporation to leave N- (l-methylhexyl) aniline (.76 parts, 37%). ia) In an alternative procedure, the N- (1-methylhexyl) aniline was prepared as follows: To a stirred, ice-cooled mixture of 28 parts of aniline, 69 parts of heptan-2-one and 9 parts of propionic acid, 9.8 parts of sodium borohydride were added in portions at a rate such as to maintain the temperature at less than 5 ° C. The reaction mixture was allowed to warm to room temperature and was stirred overnight. The reaction mixture was then poured into a mixture of ice water, and extracted with ethyl acetate. The organic phase was washed with water, with 2% hydrochloric acid and with water. The dried organic phase was evaporated to leave N- (1-methylhexyl) aniline (53.5 parts, 93%). ii) A mixture of 76 parts of N- (1-methylhexyl) aniline, 66 parts of 1-bromobutane, 65 parts of anhydrous potassium carbonate and 150 parts of DMF was stirred while heating to reflux for 41 hours. An additional 44 parts of 1-bromobutane was added and the mixture was stirred while heating to reflux for an additional 19 hours. The cooled mixture was poured into 400 parts of water and the organic phase was separated. The aqueous phase was extracted with toluene, the organic phases and the toluene extract were combined and washed with water (2 x 100 parts) before evaporating to leave N-butyl-N- (1-methylhexyl) aniline (72.8 parts, 44%) which were purified by vacuum distillation to give N-butyl-N- (1-methylhexyl) ) aniline, boiling point 73-80 ° C, 2.6 mm hg. [Pigment (1)]. iia) In an alternative procedure, N-butyl-N- (1-methylhexyl) aniline was prepared as follows: A mixture of 7.45 parts of N-butylaniline, 7.5 parts of anhydrous p.otasium carbonate, 13.5 parts of 2-bromoheptane and 25 parts of dimethylformamide was stirred at 130 ° C for 86 hours. The reaction mixture was poured into water, saturated with salt and extracted with ethyl acetate. The organic phase was washed with water, dried over magnesium sulfate and evaporated to leave N-butyl-N- (1-methylhexyl) aniline (11.8 parts, about 60% strength). To this material 10 parts of acetic anhydride had been added before further use. iii) A stirred mixture of the disodium salt of 4-cyano-5-dicyanomethylidene-3-hydroxy-2-oxo-2,5-dihydropyrrole (23 parts) and anhydrous N, N-dimethylformamide (180 parts) was cooled to - 5 ° C at -10 ° C and acetic anhydride containing Nn-butyl-N- (1-methylhexyl) aniline (27%, 37 parts) was added by dropwise addition of 26 p-phosphorus oxychloride arts while The temperature was maintained below -5 ° C. The mixture is. allowed to warm to room temperature and stirred for 20 hours. The reaction mixture was poured into a stirred mixture of ice and water (400 parts) and 400 parts of acetone was added before filtering a solid. The solid was repeatedly washed with hot water (40 ° C) and then dried at 50 ° C to produce 3- (4- (N-butyl-N- (1-methylhexyl) amino) phenyl) -4-cyano- 5-dicyanomethylidene-2-oxo-2,5-dihydropyrrole (26.8 parts, 65%). A small sample of this material was suspended in boiling methanol, collected by filtration, washed with methanol and dried at 50 ° C to give 3- (4- (Nn-butyl-N- (1-methylhexyl) amino ) phenyl) -4-cyano-5-dicyanomethylidene-2-oxo-2,5-dihydropyrrole, melting point 180 ° C; ? max (CH2C12) 662nm. (e ax 60231); M / Z (El) 415 (M + f 20%), 400 (15), 372 (12), 344 (100), 288 (33) and 272 (25).
Example 2 - Pigment (2) anthraquinone type A pigment 22 obtained commercially as IC Disperse Blue 60 is a mixture of 13.5 parts by weight of Palanil BG-ME Blue and 25 parts by weight of Palanil Blue BG-M, the mixture of which is completed up to 100 parts by weight with agents dispersants. The pigments have the following respective structures.
Bright Blue by Palanil BG-M Blue Brillan-te by Palanil BG-ME Examples 3-4 Preparation of Mixtures Example 3 A pigment (1) was synthesized as described in Example 1, which contained less than 10% by weight of the corresponding N, N-dibutyl compound as an impurity. A press-dough of this pigment was ground with spheres as a 40% aqueous suspension with 20 parts of a stable dispersing agent at high temperature until the pigment particle size (average diameter) is in the range of 0.1-5. micrometers A pigment (2),. as described in Example 2, it is constituted in a paste made by pressing, which is also ground by spheres in the same way as a pigment (1).
Each of the ground pastes of the pigments (1) and (2) are combined with each other and the dispersion is standardized to a liguid containing 20.5% of the mixture, by adding 6.5 parts of a humectant and water (up to 100 parts). This is especially suitable for use in direct printing and continuous pigmentation of polyester and polyester / cellulose blends and can also be used for escape pigmentation. The same dispersion is standardized to a solid mark, which it contains. 12 parts of pigment (1), 29 parts of pigment (2) and 59 parts of dispersing agent, by the addition of 39 parts of a dispersion agent stable to temperature and drying either to a grain or powder form in a spray dryer. The product is especially suitable for escape pigmentation of polyester, polyester / cellulose and polyester / wool blends, and can also be used for continuous pigmentation and direct printing.
Example 4 Example 3 is repeated except that 100 parts of the spray dried grains contain 6 parts of the pigment (11 and 33 parts of the pigment (2).
Examples 5-6 A pigmentation bath for the escape pigment of the polyester in the form of parts is prepared by the addition of 3 ml of an aqueous dispersion of the solid composition of examples 3 and 4 respectively (1 g of pigment in 100 ml of water to 40-50 ° C) to 55.8 ml of deionized water and 1.2 ml of buffer solution. A piece of 5 g of polyester is added to this pigmentation bath and the whole is maintained for 45 minutes at 130 ° C in a Werner Mathis Labomat high-temperature pigmentation machine.
After rinsing with water and a clarification treatment by reduction,. the material is pigmented with a bright greenish-blue shade with excellent light build-up and firmness.

Claims (23)

1. A pigment mixture, comprising: (A) at least one pyrroline pigment of the formula (I) (I) wherein R1 is hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 2 to 20 carbon atoms; and D is aryl; and (B) at least one pigment of the anthraquinone type of the formula (II) II) where RB is (CH2) nORB1; RB1 is a group (alkoxy, of 1 to 6 carbon atoms) - (albuilo of 1 to 6 carbon atoms) or alguilo of 1 to 6 carbon atoms; n is l-6; and ZB is O or NH.
2 . A pigment mixture according to claim 1, wherein in a pigment of the formula (I) of the mixture, D is a group of the formula (a) wherein each of R2 and R3 is independently an alkyl, cycloalkyl, aryl, alkenyl, or aralkyl group.
3. A mixture of pigments according to claim 2, wherein D is a group of the formula (a), R 2 is as defined in claim 2 and R 3 is alkenyl of 7 to 20 carbon atoms.
4. A mixture of pigments according to claim 3, wherein R2 is C4H9 and R3 is 1-methyl-n-hexyl.
5. A pigment mixture according to claim 4, wherein the component (A) is a pyrroline pigment (A1) of the formula (I) wherein R1 is hydrogen, R2 is C4H9 and R3 is 1-methyl-n- hexyl or is a mixture of the pigment type pyrroline (A1) with a pigment type pirrolina (A2) of the formula (I) where R1 is hydrogen and each of R2 and R3 is C4H9, whose mixture of pigment type pyrroline contains up to 10% by weight of the total weight of the pyrroline pigment mixture, of the pigment (A)
6. A pigment mixture according to claim 3, wherein the component (A) is a pyrroline pigment (A3) or (A4), each of the formula (I) or is a mixture of the pigments (A3) and (A4), whose pigment (A3) is a pigment where R1 is hydrogen, R2 is ethyl and R3 is n-octyl and whose pigment (A4) is a pigment where R1 is hydrogen, R2 is ethyl and R3 is 2-ethyl- n-hexyl.
7. A mixture of pigments according to claim. 2, wherein D is a group of the formula (a), R 2 is as defined according to claim 2 and R 3 is alkenyl of 1 to 6 carbon atoms.
8. A mixture of pigments according to claim 7, wherein R1 is hydrogen or allyl, R2 is 3-phenyl-n-propyl and R3 is C4H9.
9. A mixture of pigments according to any preceding claim, wherein the component (B) is at least one of the anthraguinone type pigments (B1), (B2) and (B3), each of the formula (II) wherein ZB is oxygen and n is 2 or 3, in which pigment (B1), RB1 is methyl, in which pigment (B2), RB1 is methoxyethyl; and in which pigment (B3), RB1 is ethyl.
10. A pigment mixture according to claim 9, which is a mixture of each of the pigments (B1), (B2) and (B3).
11. A pigment mixture according to claim 9, wherein the component (B) is a mixture of the anthraquinone type pigments (B1) and ; B2).
12. A pigment mixture according to claim 11, wherein the weight ratio of the pigment (B1) pigment (B2) is from 30:70 to 60:40 inclusive.
13. A mixture of pigments according to claim 12, wherein the proportion of the pigment (B1) :( B2) is from 45:55 to 48:52.
14. A mixture of pigments according to any preceding claim, wherein the weight ratio of component (A): component (B) is from 3:97 to 60:40 inclusive.
15. A mixture of pigments according to claim 14, wherein the proportion of component (A): component (B) is from 8:92 to 35:65 inclusive.
16. A pigment mixture according to claim 1, wherein component (A) is a pyrroline pigment of the formula (I), wherein R 1 is hydrogen, R 2 is C 4 H 9 and R 3 1-methyl-n-hexyl or a mixture thereof, with up to 10% by weight of a pyrroline-type pigment of the formula (I) wherein R1 is hydrogen and each of R2 and R3 is C4H9, and the component (B) is a mixture of anthraquinone-type pigments ( B1) and (B2), given and defined in claim 9.
17. A mixture of pigments according to claim 16, wherein the ratio of component (A): component CB) is 10:90 to 30:70.
18. A mixture of pigments according to claim 17 ,. where the ratio is 6:33.
19. A mixture of pigments according to any of claims 16 to 18, wherein the weight ratio of the pigment (B1): (B2) is from 45:55 to 48:52.
20. A composition comprising a mixture of pigments according to any of the preceding claims, and at least one dispersing agent, surfactant or wetting agent.
21. A process for coloring a synthetic textile material or a mixture of fibers thereof, which comprises applying to it a mixture of pigments according to any of claims 1 to 19.
22. A process for coloring a synthetic textile material or a mixture of fibers thereof, which comprises applying thereto a composition according to claim 20, dispersed in an aqueous medium.
23. A process according to claim 21 or claim 22, wherein the synthetic textile or blend of fibers thereof is a polyester or a polyester-cellulose or polyester-wool mixture.
MXPA/A/2001/003120A 1998-10-13 2001-03-26 Disperse dye mixtures MXPA01003120A (en)

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GB9822336.5 1998-10-13

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MXPA01003120A true MXPA01003120A (en) 2002-02-26

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