WO2018114140A1

WO2018114140A1 - Inks and a process for ink-jet printing textile fibre materials

Info

Publication number: WO2018114140A1
Application number: PCT/EP2017/079026
Authority: WO
Inventors: Joachim WEIHRATHER; Marc Burglin; Lukas BROLL; Dominique-Marcel SERAFINI
Original assignee: Huntsman Advanced Materials (Switzerland) Gmbh
Priority date: 2016-12-20
Filing date: 2017-11-13
Publication date: 2018-06-28

Abstract

The present invention relates to an aqueous ink comprising (A) at least one disperse dye, and (B) a surfactant system comprising a mixture of (b1) at least one first surfactant of the formula (1),and (b2) at least one second surfactant selected from the group alkoxylated castor oil and tristyrylphenol alkoxylate of the formula (2) wherein Q₁ and Q₂ each independently of the other is C₁-C₁₂alkyl, which is branched or unbranched, B and E are each independently of the others a radical of the formula -O-CH₂-CH₂-, -O-CH(CH₃)-CH₂- or -O-CH₂-CH(CH₃)-, G means hydrogen, sulfo (-SO₃H) or phosphato (-PO₃H₂) or a salt thereof, the sum of m+n is a number of from 1 to 40, and I is a number of from 1 to 40. The ink is stable and shows a good run-ability on inkjet printers. Prints obtained on semi-synthetic or synthetic hydrophobic textile fibre materials exhibit high temperature light fastness and at the same time a high colour strength.

Description

Inks and a process for ink-jet printing textile fibre materials

The present invention relates to aqueous inks comprising disperse dyestuffs and a surfactant system, and to a process for printing semi-synthetic or synthetic hydrophobic textile fibre materials with the said inks by an ink-jet printing process.

Ink-jet printing inks and processes have already been used for some years in the textile industry. They make it possible to do without the otherwise customary production of a printing stencil, so enabling considerable savings to be made in both cost and time. In connection with the production of originals, in particular, it is possible to respond to changes within a much shorter time.

Appropriate ink-jet printing inks should have optimum performance characteristics. In this context mention may be made of characteristics such as stability and run-ability. In addition, heightened requirements are placed on the quality of the resulting prints, in terms, for example, of colour strength, fibre-dye bond stability, and wet fastness properties. Nowadays appropriate inks are expected to fully satisfy the highest demands, especially in respect of high temperature light fastness and colour strength of the prints prepared with such inks. However, aqueous inks that yield tinctorially strong prints and that exhibit good allround fastness properties, unfortunately, show either insufficient stability or poor run-ability, or even both characteristics do not reach the desired standard. Aqueous printing inks having superior properties in these respects are required, in particular, in automotive industry for car interior lining and seat covers, but also for other applications such as outdoor and for flags and banners.

The present invention accordingly relates to an aqueous ink comprising

(A) at least one disperse dye, and

(B) a surfactant system comprising a mixture of

(b1 ) at least one first surfactant of the formula

HO-B— C— C≡C— C— B— OH

^{C H}3 ^{C H}3 (1 ), and

(b2) at least one second surfactant selected from the group alkoxylated castor oil and tristyrylphenol alkoxylate of the formula

wherein

Q₁ and Q₂ each independently of the other is CrC₁₂alkyl, which is branched or unbranched,

B and E are each independently of the others a radical of the formula -O-CH₂-CH₂-, -0-CH(CH₃)-CH₂- or -0-CH₂-CH(CH₃)-,

G means hydrogen, sulfo (-S0₃H) or phosphato (-P0₃H₂) or a salt thereof, the sum of m+n is a number of from 1 to 40, and

I is a number of from 1 to 40.

As the at least one disperse dye (A) there come into consideration for the inks of the present invention, for example, C.I. Disperse Yellow 42, 49, 71 , 76, 83, 88, 93, 99, 1 14, 1 19, 126, 160, 163, 165, 180, 183, 186, 198, 199, 200, 224, 237, and 251 ; C.I. Disperse Orange 29, 30, 31 , 38, 42, 44, 45, 53, 54, 55, 71 , 73, 80, 86, 96, 1 18, 1 19, and 157; C.I. Disperse Red 73, 88, 91 , 92, 1 1 1 , 127, 131 , 143, 145, 146, 152, 153, 154, 179, 191 , 192, 206, 221 , 258, 279, 283, 302, 323, 328, 359, and 386; C.I. Disperse Violet 26, 35, 48, 56, 57, 77 and 97; C.I. Disperse Blue 27, 54, 60, 73, 77, 79, 79:1 , 87, 143, 153, 165, 165:1 , 165:2, 181 , 185, 197, 225, 257, 266, 267, 281 , 341 , 353, 354, 358, 364, 365, and 368; and other disperse dyes suitable to satisfy required hue, colour strength and fastness properties.

The above disperse dyes are commercially available and may be in a powder or lump dry state or in a wet cake or slurry state. They optionally contain a small amount of a dispersing agent to suppress dye particle aggregation during or after synthesis. Preferably the dyes have a smaller particle size. Suitably, they can be used as a dye for black by appropriately mixing yellow, orange and red dyes and a main blue dye. Furthermore, other dyes may be added to adjust hue.

The aqueous ink according to the present invention further comprises as component (B) a surfactant system comprising a mixture of at least one first surfactant (b1 ) and at least one second surfactant (b2). As the at least one first surfactant (b1 ) a non-ionic acetylene diol/alkoxylated acetylene diol of formula (1 ) is used. The at least one second surfactant (b2) is selected from the group alkoxylated castor oil and tristyrylphenol alkoxylate of the formula (2).

In one embodiment of the present invention the at least one first surfactant (b1 ) is a low alkoxylated acetylene diol of formula (1 ), which beside the alkoxylated acetylene diol may contain the acetylene diol in a small amount, wherein the hydroxyl groups are attached directly to the acetylene hydrocarbon chain of the acetylene, that is the compound of formula (1 ), wherein the sum of m+n is the number 0. The alkoxylated acetylene diol may be obtained from the acetylene diol by alkoxylation using customary methods known in the art. The alkoxylate chains of the alkoxylated acetylene diol may be of various lengths and comprise various alkoxylates selected from ethoxylates and propoxylates. The indicated numbers m+n are thus average values. Typically, the acetylene alkoxylate comprises a terminal hydroxyl group attached to each alkoxylate chain.

As the radicals Q₁ and Q₂ of the at least one first surfactant (b1 ) of formula (1 ) there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-decyl and n- dodecyl.

Preferably, Qi and Q₂ each independently of the other is d-Cealkyl, which is branched or unbranched, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, neopentyl or n-hexyl. In a certain embodiment Q₁ and Q₂ are n-butyl, isobutyl, sec-butyl or tert-butyl.

Preferably, B of the at least one first surfactant (b1 ) of formula (1 ) are each a radical of the formula -0-CH₂-CH₂-.

Preferably, the sum of m+n is a number of from 1 to 20, especially of from 1 to 10.

As the at least one first surfactant (b1 ) there come into consideration commercially available surface-active acetylene derivatives which are known under the trade name Surfynol^® (Air Products). Examples are ethoxylated derivatives of tetramethyldecynediol which are available as Surfynol^® 420, Surfynol^® 440, Surfynol^® 465, and Surfynol^® 485. In an interesting embodiment Surfynol^® 420, specified by manufacturer as a low ethoxylated 2,4,7,9- tetramethyl-5-decyne-4,7-diol, HLB=4, is used as the at least one first surfactant (b1 ).

The alkoxylated castor oils suitable as the at least one second surfactant (b2) are those containing, for example, at least about 5 moles ethylene oxide per mole castor oil. Preferred are those containing 25 to 200 moles ethylene oxide, preferably 30 to 50 moles, especially 35 to 45 moles. The castor oil base may be hydrogenated or non-hydrogenated. The alkoxylation of such castor oils with ethylene oxide is well known in the art and the oils useful herein are not limited by their method of preparation. Ethoxylated castor oils containing up to about 200 moles ethylene oxide are available commercially. It is contemplated that the alkoxylation may also be performed using similar levels of propylene oxide. Suitable alkoxylated castor oils are available, for example, under the trade names Agnique^® (BASF) and Drehscofix^® (Huntsman). In an interesting embodiment Agnique^® CSO 35 or Drehscofix^® CO 140 is used as the at least one second surfactant (b2).

The tristyrylphenol alkoxylates also suitable as the at least one second surfactant (b2) generally are mixtures of several compounds which differ by the degree and position of substitution of the phenyl ring and the number of ethoxylate and/or propoxylate units. Such tristyrylphenol alkoxylates are appropriately depicted by formula (2). The indicated numbers I are thus average values. The alkoxylated tristyrylphenols may be obtained from the tristyrylphenols by alkoxylation using customary methods known in the art. Typically, the amount of ethoxylate and/or propoxylate is 5-40 mol, preferably 5-20 mol per mol of tristyrylphenol.

In one embodiment, I is a number of from 5 to 20.

Preferably, E of the at least one second surfactant (b2) of formula (2) is ethoxylate, that is a radical of the formula -0-CH₂-CH₂-.

The tristyrylphenol alkoxylate sulfates or phosphates can be used in free acid form, that is G is sulfo (-SO₃H) or phosphato (-P0₃H₂), or in salt form. Suitable salts of the tristyrylphenol alkoxylate sulfates or phosphates are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium calcium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono- , di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propylamine, or a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine.

In one embodiment tristyrylphenol alkoxylate sulfates or phosphates are used in free acid form and the acid is appropriately neutralized in the ink vehicle to a pH, for example, of from 8.5 to 9.0 to minimize the content of salt in the ink. Phosphate esters of tristyrylphenol alkoxylates are preferred. If tristyrylphenol alkoxylate sulfates or phosphates are in salts form, salts with ammonia, amines, as triethylamine and triethanolamine, calcium, potassium and sodium are preferred.

As the at least one second surfactant (b2) there come into consideration commercially available tristyrylphenol alkoxylates of formula (2), which are known under the trade name Soprophor^® ( hodia). Examples are tristyrylphenol ethoxylates which are available as Soprophor^® S/25, CY/8 and BSU, all specified by manufacturer as ethoxylated

tristyrylphenol; Soprophor^® 3D33, specified by manufacturer as tristyrylphenol ethoxylate phosphate ester; Soprophor^® FL and FL/60 specified by manufacturer as ethoxylated polyarylphenol phosphate amine salt; and Soprophor^® FLK specified by manufacturer as ethoxylated polyarylphenol phosphate potassium salt. In an interesting embodiment

Soprophor^® 3D33 is used as the at least one second surfactant (b2).

In an interesting embodiment the surfactant system (B) comprises

(b1 ) a low ethoxylated surfactant of the formula (1 ), wherein Q₁ and Q₂ are independently of the other n-butyl, isobutyl, sec-butyl, preferably isobutyl, B are each a radical of the formula - O-CH₂-CH₂-, and the sum of m+n is a number of from 1 to 20, especially of from 1 to 10, and (b2) an ethoxylated castor oil containing 30 to 50 moles of ethylene oxide

In another interesting embodiment the surfactant system (B) comprises

(b1 ) a low ethoxylated surfactant of the formula (1 ), wherein Q₁ and Q₂ are independently of the other n-butyl, isobutyl, sec-butyl, preferably isobutyl, B are each a radical of the formula - O-CH₂-CH₂-, and the sum of m+n is a number of from 1 to 20, especially of from 1 to 10, and (b2) a tristyrylphenol ethoxylate phosphate ester of formula (2), wherein E is a radical of the formula -0-CH₂-CH₂-, G is phosphato and I is a number of from 5 to 20. The amount of surfactant system (B) in the aqueous ink according to the present invention is, for example, of from 0.1 to 2% by weight, preferably 0.8 to 1.2% by weight, based on the total weight of the aqueous ink. Appropriately, the first surfactant (b1 ) is used in an amount of 5 to 80% by weight, preferably 10 to 50% by weight, especially 15 to 30% by weight, based on the total amount of surfactant system (B), that is the total amount of the first surfactant (b1 ) and the second surfactant (b2).

In a particular embodiment of the present invention, the at least one disperse dye (A) comprises

wherein

R₁ is C C₁₂alkyl, or C₂-C₁₂alkyl interrupted by one or more oxygen atoms and/or -COO- groups, and

R₂, R3, R4 and R₅ each independently of the others is hydrogen, Ci-Ci₂alkyl, chlorine, bromine, hydroxy or amino;

wherein

R6 is hydrogen, bromine, chlorine or cyano,

R₇ is trifluoromethyl, bromine or chlorine,

R₈ is hydrogen, methyl or acetylamino, Rg and R₁0 each independently of the other is Ci-C4alkyl unsubstituted or substituted by cyano or by acyloxy, one of the C C₄alkyl radicals R₉ and R₁₀ is substituted by cyano or by acyloxy; and

wherein

Rii is fluoro, trifluoromethyl, trifluoromethoxy, trifluoromethylsulfonyl or cyano,

R₁₂ and R₁₃ each independently of the other represent hydrogen, CrC₁₂alkyl, CrC₁₂alkoxy, halogen, cyano, nitro, trifluoromethyl or -COORi6, wherein R₁₆ is Ci-Ci2alkyl unsubstituted or substituted by one or more Ci-Ci2alkoxy, hydroxy, amino or halogen, and

one of the radicals R₁₄ and R₁₅ denotes hydrogen or CrC₆alkyl unsubstituted or substituted by hydroxy, C C₄acyloxy, C C₆alkoxy, CrC₄acyloxy-CrC₆alkoxy or hydroxy-C C₆alkoxy, and the other one of the radicals R14 and R15 denotes Ci-C6alkyl unsubstituted or substituted by phenoxy-CrC₆alkoxy, or phenyl that is unsubstituted or substituted by one or more substituents from the group CrC₁₂alkyl, CrC₁₂alkoxy and trifluoromethyl.

In another embodiment the aqueous inks comprising dyestuff components (a1 ), (a2) and (a3) indicated above further comprise

(a4) at least one dye of the formula

wherein

one of the radicals R17 and Ris denotes hydroxy and the other one of the radicals R17 and Ris denotes amino or nitro,

R₁₉ is hydrogen or phenyl unsubstituted or substituted by one or more substituents from the group hydroxy and C C₆alkoxy, and

R₂0 denotes hydrogen or phenyl that is unsubstituted or substituted by one or more substituents from the group hydroxy, halogen, C Cealkoxy or CrC₆alkyl unsubstituted or substituted by hydroxy. 1 in the meaning of C₂-C₁₂alkyl interrupted by one or more oxygen atoms and/or -COO- groups is, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-(2- ethoxyethoxy)ethyl, -CH₂CH₂OCH₂CH₂OCH₃, -CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₃, -CH₂CH₂0 CH₂CH₂OCH₂CH₂OC₂H₅, -CH₂CH₂COOCH₃, -CH₂CH₂COOC₂H₅, -CH₂CH₂CH₂CH₂COOCH₃, -CH₂CH₂CH₂CH₂COOC₂H₅,

-CH₂CH₂OCH₂CH₂COOCH₃ or -CH₂CH₂OCH₂CH₂COOC₂H₅.

Ri, R2, R3, R4, R5, R12, Ri3, Ri4, Ri5 and R₁₆ each in the meaning of C C₁₂alkyl , or any of C C₁₂alkyl bound to R₁₄ and R₁₅ in the meaning of phenyl may be straight-chain or branched. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-decyl and n- dodecyl.

Rg and R10 each in the meaning of Ci-C4alkyl may be straight-chain or branched , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, at least one of the C C₄alkyl radicals R₉ and R₁₀ is substituted by cyano or by acyloxy, for example, acetyloxy or propionyloxy, preferably, acetyloxy.

R₁₂ and R₁₃ each in the meaning of C C₁₂alkoxy, or any of C C₁₂alkoxy bound to R₁₄ and R₁₅ in the meaning of phenyl may be straight-chain or branched . Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n- pentyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, n-decyloxy and n- dodecyloxy.

R₁₂ and R₁₃ each in the meaning of halogen substituents are, for example, fluorine, chlorine or bromine, and especially chlorine or bromine.

Ri4 and R₁₅ each in the meaning of CrC₆alkyl may be unsubstituted or substituted by hydroxy, CrC₄acyloxy, CrC₆alkoxy, Ci-C4acyloxy-Ci-C₆alkoxy, hydroxy-Ci-C₆alkoxy or phenoxy-Ci-C6alkoxy. Substituted alkyl groups are, for example, 2-hydroxyethyl, 2- hydroxypropyl , -(CH₂)₂-0-(CH₂)₂-OH, -(CH₂)₃-0-(CH₂)₄-OH, -(CH₂)₂-0-acyl, -(CH₂)₃-0-acyl, - CH₂-CH(CH₃)-0-acyl, -(CH₂)₆-0-acyl, -(CH₂)₂-0-(CH₂)₂-0-acyl, -(CH₂)₃-0-(CH₂)₄-0-acyl, - (CH₂)2-0-(CH₂)2-0-phenyl, -(CH₂)₃-0-(CH₂)2-0-phenyl, -(CH₂)₃-0-(CH₂)₄-0-phenyl, 2- methoxyethyl, 3-methoxypropyl, 2-ethoxyethyl and 3-ethoxypropyl; acyl meaning, for example, formyl, acetyl or propionyl; and phenyl meaning C₆H₅.

Ri6 in the meaning of C C₁₂alkyl may be unsubstituted or substituted by one or more C C₁₂alkoxy-, hydroxy-, amino- or halogen-radicals. Substituted alkyl groups are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxy butyl, 2-aminoethyl, 2-aminopropyl, 4-aminobutyl,

2- chloroethyl, 2-bromoethyl, 4-chlorobutyl, 2-methoxyethyl, 3-methoxypropyl, 2-ethoxyethyl and 3-ethoxypropyl.

CrC₆alkyl bound to R₂₀ in the meaning of phenyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl or n-hexyl, each of which is unsubstituted or substituted by hydroxy.

CrC₆alkoxy bound to R₁₉ and R₂₀ in the meaning of phenyl is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy or n-hexyloxy.

Halogen bound to R₂₀ in the meaning of phenyl is, for example, fluorine, chlorine or bromine, and especially chlorine or bromine.

Preferably, R₁ is ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl or

3- isopropoxypropyl, and especially n-propyl, n-butyl, isobutyl or n-hexyl.

Preferably, R₂ and R₃ are identical and are each hydrogen, chlorine or bromine.

Preferably, R₄ and R₅ each independently of the other represent hydrogen or chlorine.

In a particular embodiment, R₂, R₃, R₄ and R₅ are each hydrogen.

Preference is given to inks that comprise, as dyestuff component (a1 ), at least one dye of formula (3), wherein R₁ is ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl or

3-isopropoxypropyl and R₂, R₃, R₄ and R₅ are as defined and preferred hereinabove and, especially, each of R₂, R₃, R and R₅ is hydrogen. Preferably, ₆ is bromine, chlorine or cyano, especially bromine or chlorine, and more especially bromine.

Preferably, R₇ is trifluoromethyl or chlorine, and especially trifluoromethyl. Preferably, R₈ is hydrogen or acetylamino, and especially hydrogen. Preferably, R₉ is cyanoethyl. Preferably, R₁₀ is cyanoethyl.

Preference is given to inks that comprise, as dyestuff component (a2), at least one dye of formula (4) wherein

R₆ is bromine or chlorine, and more especially bromine,

R₇ is trifluoromethyl or chlorine, and especially trifluoromethyl,

R₈ is hydrogen or acetylamino, and especially hydrogen, and

R₉ and R₁₀ are cyanoethyl.

Preferably, Rn is fluoro, trifluoromethyl or cyano, epecially trifluoromethyl or cyano, and more especially trifluoromethyl.

Preferably, R12 and R13 each independently of the other represent hydrogen, fluoro, chloro, bromo, cyano or nitro, especially hydrogen or nitro.

Preferably, one of the radicals R₁₄ and R₁₅ denotes hydrogen or CrC₆alkyl unsubstituted or substituted by hydroxy or hydroxy-CrC₆alkoxy, and the other one of the radicals R₁₄ and R₁₅ denotes CrC₆alkyl unsubstituted or substituted by phenoxy-CrC₆alkoxy, or phenyl that is unsubstituted or substituted by one or more substituents from the group trifluoromethyl, n- propyl, n-butyl and n-butoxy.

Especially, one of the radicals R14 and R15 denotes hydrogen, 2-hydroxyethyl or the radical of formula -(CH₂)2-0-(CH₂)2-OH, and the other one of the radicals R₁₄ and R₁₅ denotes the radical of formula -(CH₂)3-0-(CH₂)2-0-phenyl, or phenyl that is unsubstituted or substituted by one or more substituents from the group trifluoromethyl, n-propyl, n-butyl and n-butoxy, and more especially one of the radicals R₁₄ and R₁₅ denotes hydrogen, and the other one of the radicals R₁₄ and R₁₅ denotes phenyl.

Preference is given to inks, wherein the dye of formula (5) is represented by a dye of formula

wherein

the radicals Rn , R₁₂, R13, R14 and R₁₅ have the meanings and preferred meanings given above.

Preference is given to inks that comprise, as dyestuff component (a3), at least one dye of formula (5a), wherein

R11 is trifluoromethyl or cyano,

R12 and Ri3 each independently of the other represent hydrogen, fluoro, chloro, bromo, cyano or nitro, especially hydrogen or nitro,

one of the radicals R₁₄ and R₁₅ denotes hydrogen, 2-hydroxyethyl or the radical of formula - (CH2)2-0-(CH₂)2-OH, and the other one of the radicals R14 and R15 denotes the radical of formula -(CH₂)3-0-(CH₂)2-0-phenyl, or phenyl that is unsubstituted or substituted by one or more substituents from the group trifluoromethyl, n-propyl, n-butyl and n-butoxy, and more especially one of the radicals R₁₄ and R₁₅ denotes hydrogen, and the other one of the radicals R_M and R15 denotes phenyl.

Suitable dyestuff components (a1 ) are, for example, the dyes of formulae (301 ) to (327):

The inks according to the invention comprise as dyestuff component (a1 ), preferably two or three, and especially three different dyes of formula (3), for example, the yellow dyes of formulae (301 ), (302) and/or (303).

The dyes of formula (1 ) are known per se, or they can be prepared in analogy to known compounds. The dyes of formula (1 ) are described, for example, in EP-A-43937 and US-A- 7544217.

Suitable dyestuff components (a2) are, for example, the dyes of formulae (401 ) to (41 1 ):

The inks according to the invention comprise as dyestuff component (a2), for example, the orange dye of formulae (401 ) or (402).

The dyes of formula (4) are known per se, or they can be prepared in analogy to known compounds. The dyes of formula (4) are described, for example, in US-A-6540794. Suitable dyestuff components (a3) are, for example, the dyes of formulae (501 ) to (525):

- 19-

The inks according to the invention comprise as dyestuff component (a3) two different dyes of formula (5), for example, the red dyes of formulae (501 ) and (502), or the red dyes of formulae (503) and (504). The dyes of formula (5) are known per se, or they can be prepared in analogy to known compounds. The dyes of formula (5) are described, for example, in WO-A-2012/084417.

Suitable dyestuff components (a4) are, for example, the compounds of formulae (601 ) to (606):

In some embodiments, the aqueous inks comprise as dyestuff component (a4) the blue dyes of formulae (601 ) and (602), the blue dyes of formulae (603) and (604), or the blue dyes of formulae (603) and (605), and preferably the blue dyes of formulae (601 ) and (602).

The dyes of formula (6) are known per se, or they can be prepared in analogy to known compounds.

The inks according to the present invention may comprise one or more further dyestuff components, for example, one or two dyestuff components, to adjust the color shade or other

The dyes of formula (7), (8) and (9) are known per se, or they can be prepared in analogy to known compounds.

The inks generally have an overall content of disperse dyestuffs of from 1 to 20% by weight, in particular from 1 to 10% by weight and, above all, from 1 to 8% by weight, based on the overall weight of the ink composition.

The content of each disperse dyestuff depends on the desired color shade. Suitable black or grey inks comprise, for example,

0.70 to 1 .00% by weight of dyestuff component (a1 ),

0.85 to 1 .15% by weight of dyestuff component (a2),

1 .10 to 1 .50% by weight of dyestuff component (a3) and

3.15 to 4.35% by weight of dyestuff component (a4),

based on the overall weight of the ink composition.

Advantageously, the inks of the present invention contain the disperse dyes in a finely dispersed form. For this purpose the disperse dyes are milled to an average particle size of between 0.1 and 10 microns, preferably between 1 and 5 microns and, with particular preference, between 0.5 and 2 microns. Milling can be carried out in the presence of dispersing agents. For example, the dried disperse dye is milled with a dispersing agent or kneaded in paste form with a dispersing agent and, if desired, is dried under reduced pressure or by spraying. The resulting preparations can be used to prepare the inks of the invention by addition of water and, if desired, of further auxiliaries.

Suitable dispersing agents are anionic dispersing agents, for example, from the group consisting of

(a) polystyrenesulfonates, (b) fatty acid taurides,

(c) alkylated diphenyl oxide mono- or disulfonates,

(d) sulfonates of polycarboxylic esters,

(e) an adduct of from 1 to 60, preferably from 2 to 30, mol of ethylene oxide and/or propylene oxide with fatty amines, fatty amides, fatty acids or fatty alcohols each having 8 to 22 carbon atoms or with trihydric to hexahydric alkanols having 3 to 6 carbon atoms, the said adduct being converted into an acidic ester with an organic dicarboxylic acid or with an inorganic polybasic acid,

(f) ligninsulfonates,

(g) naphthalenesulfonates, and

(h) formaldehyde condensates.

As ligninsulfonates (f) use is made primarily of those ligninsulfonates, or their alkali metal salts, whose content of sulfo groups does not exceed 25% by weight. Preferred

ligninsulfonates are those having a content of from 5 to 15% by weight of sulfo groups. Such ligninsulfonates are marketed, for example, as eax 81A, Reax 83A, Reax 85A, Reax 88B, Reax 905, Reax 907, Hyact, Marasperse N.

Examples of suitable formaldehyde condensates (h) are condensates of ligninsulfonates and/or phenol and formaldehyde, condensates of formaldehyde with aromatic sulfonic acids, such as condensates of ditolyl ether sulfonates and formaldehyde, condensates of naphthalenesulfonic acid with formaldehyde and/or of naphthol- or naphthylaminosulfonic acids with formaldehyde, condensates of phenolsulfonic acids and/or sulfonated

dihydroxydiphenyl sulfone and phenols or cresols with formaldehyde and/or urea, and condensates of diphenyl oxide disulfonic acid derivatives with formaldehyde.

Interesting products (h) are

- condensates of ditolyl ether sulfonates and formaldehyde, as described for example in US- A-4,386,037,

- condensates of phenol and formaldehyde with ligninsulfonates, as described for example in US-A-3,931 ,072,

- condensates of 2-naphthol-6-sulfonic acid, cresol, sodium bisulfite and formaldehyde [cf. FIAT Report 1013 (1946)], and

- condensates of diphenyl derivatives and formaldehyde, as described for example in US-A- 4,202,838. ln one embodiment compound (h) is the compound of the formula

in which

D is a direct bond or oxygen,

A is the radical of an aromatic compound and is attached to the methylene group by a ring carbon atom,

M is hydrogen or a salt-forming cation, such as an alkali metal, alkaline earth metal or ammonium, and

q and p independently of one another are a number from 1 to 4.

In another embodiment compound (h) is a compound based on the sulfonated condensate of a chlorometh lbiphenyl isomer mixture and naphthalene, of the formula

in which (SC^Na)^.^ denotes an average degree of sulfonation of from 1.4 to 1.6.

The above dispersants are known and commercially available, or can be prepared in analogy to known compounds by widely known processes.

Apart from the disperse dyes and the dispersants, the inks may include thickeners to adjust the viscosity. There come into consideration thickeners of natural or synthetic origin, examples being commercial alginate thickeners, starch ethers or locust bean gum ethers, especially sodium alginate on its own or in a mixture with modified cellulose, in particular with preferably from 20 to 25 per cent by weight of carboxymethylcellulose.

In the inks of the invention, preference is given to the use of synthetic thickeners such as those based on poly(meth)acrylic acids or poly(meth)acrylamides.

For the process of the invention, preference is given to inks having a viscosity of from 1 to 40 mPa.s (millipascal seconds), in particular from 1 to 20 mPa.s and, above all, from 1 to 10 mPa.s.

The inks may also include buffer substances, such as borax, borate or citrate. Examples are borax, sodium borate, sodium tetraborate, and sodium citrate. They are used in particular in amounts of from 0.1 to 3% by weight, especially from 0.1 to 1 % by weight, based on the overall weight of the ink, so as to give a pH of, for example, from 4 to 10, preferably from 5 to 8.

Further additives which may be present in the inks are surfactants other than the surfactants of surfactant system (B), redispersants and humectants.

Suitable surfactants include commercially available anionic or non-ionic surfactants. Betaine monohydrate may be mentioned as an example of a redispersant. As the humectant it is preferred to use a mixture of sodium lactate (advantageously in the form of an aqueous solution with a strength of from 50 to 60%) and glycerol and/or propylene glycol in amounts from 0.1 to 40% by weight, especially from 2 to 35 % by weight, based on the overall weight of the ink composition.

If desired, the inks may also include acid donors, such as butyrolactone or sodium hydrogen phosphate, preservatives, substances which inhibit bacterial and/or fungal growth, foam suppressants, sequestrants, emulsifiers, water-insoluble solvents, oxidizing agents, or degassing agents.

As preservatives there come into consideration formaldehyde-yielding agents, for example paraformaldehyde and trioxane, especially aqueous, approximately from 30 to 40% by weight formaldehyde solutions, imidazole compounds, for example 2-(4-thiazolyl)- benzimidazole, thiazole compounds, for example 1 ,2-benzisothiazolin-3-one or 2-n-octyl- isothiazolin-3-one, iodine compounds, nitriles, phenols, haloalkylthio compounds or pyridine derivatives, especially 1 ,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one. A suitable preservative is, for example, a 20% by weight solution of 1 ,2-benzisothiazolin-3-one in dipropylene glycol (Proxel^® GXL).

Suitable sequestrants are, for example, sodium nitrilotriacetate, sodium ethylenediamine- tetraacetate and, in particular, sodium polymetaphosphate, especially sodium hexameta- phosphate.

Suitable emulsifiers are, in particular, adducts of an alkylene oxide and a fatty alcohol, especially an adduct of oleyl alcohol and ethylene oxide.

Suitable water-insoluble solvents are high-boiling saturated hydrocarbons, especially paraffins having a boiling range from about 160 to 210°C (known as paint and varnish maker's naphthas).

A suitable oxidizing agent is, for example, an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic or -sulfonic acid, which may be in the form of an alkylene oxide adduct, especially a nitrobenzenesulfonic acid.

Suitable degassing agents are, for example, high-boiling solvents, especially turpentine oils, higher alcohols, preferably C₈ to C₁₀ alcohols, terpene alcohols or degassing agents based on mineral oils and/or silicone oils, especially commercial formulations composed of from about 15 to 25% by weight of a mineral and silicone oil mixture and from about 75 to 85% by weight of a C₈ alcohol such as 2-ethyl-n-hexanol.

The inks can be prepared in customary manner by mixing the individual constituents in the desired amount of water.

The inks are prepared, for example, by stirring the disperse dyestuff components with a dispersant and milling the resulting mixture in a wet mill to a defined degree of milling corresponding to an average particle size of from 0.2 to 1.0 μΐτη. Subsequently, the concentrated millbase - with or without the use of, for example, appropriate thickeners, dispersing agents, copolymers, surfactants, humectants, redispersants, sequestrants and/or preservatives, and also water - is adjusted to the desired concentration. To remove any coarse fractions present it is possible with advantage to carry out filtration of the ready-to-use ink through a microsieve of about 1 μΐη.

The process of the invention for printing textile fibre materials can be implemented with ink- jet printers which are known per se and are suitable for textile printing.

In the ink-jet printing process, individual drops of the ink are sprayed from a nozzle onto the substrate in a controlled manner. The methods used in this context are predominantly the continuous ink-jet method and the drop-on-demand method. In the case of the continuous ink-jet method the drops are generated continuously, with the drops that are not required for printing being diverted into a collecting vessel and, in general, recycled. In the case of the drop-on-demand method, on the other hand, the drops are generated and used for printing when desired; in other words, drops are only generated when required for printing.

Generation of the drops can be carried out advantageously, for example, by means of a piezoelectric ink-jet head or by means of thermal energy (referred to as bubble jet). For the process of the invention, preference is given to printing by the continuous ink-jet method or by the drop-on-demand method.

After printing, the fibre material is dried at temperatures of up to 150°C, preferably from 80 to 120°C

The subsequent fixing of the fibre material takes place in general by means of dry heat (thermofixing) or by means of superheated steam under atmospheric pressure (HT fixing). Fixing is carried out under the following conditions:

- Thermofixing of from 1 to 2 minutes at from 190 to 230°C;

- HT fixing of from 4 to 9 minutes at from 170 to 190°C.

The inks used in accordance with the invention can be applied to a variety of types of semisynthetic and, especially, synthetic hydrophobic fibre materials, especially textile materials. Textile materials of fabric blends that comprise such semi-synthetic or synthetic hydrophobic textile materials can likewise be printed using the inks according to the invention.

Semi-synthetic textile materials that come into consideration are especially cellulose 2½ acetate and cellulose triacetate.

Synthetic hydrophobic textile materials consist especially of linear, aromatic polyesters, for example polyesters of terephthalic acid or isophthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclo- hexane; of polycarbonates, e.g. polycarbonates obtained from a,a-dimethyl-4,4'-dihydroxy- diphenylmethane and phosgene, and of fibres based on polyvinyl chloride and on polyamide. Suitability also extends to polyester-containing mixed-fibre materials; in other words, to blends of polyester with other fibres, such as polyamide (e.g. nylon, kevlar, nomex, trogamide) and/or of polypropylene.

The present invention accordingly relates also to the use of such inks in an ink-jet printing process for printing semi-synthetic or synthetic hydrophobic textile fibre materials.

Particularly, the inks are used for the printing of polyester fibre materials or fibre materials comprising blends of polyester with other fibres, as given above.

Suitable fibres to be printed by the ink-jet printing process according to the present invention also comprise micofibres of synthetic hydrophobic textile materials, such as micofibres of polyester or polyester-containing mixed-microfibre materials. The term microfibre refers to synthetic fibres that measure less than one denier.

The inks according to the present invention are stable and at the same time show a good run-ability. The prints, for example, black and grey prints, obtainable by the process of the present invention have good all-round fastness properties. In particular, the prints have a high colour strength and a high temperature light fastness (e.g. according to VDA 75202 and SAE J 1885 as used in automotive industry). The subject matter according to the present invention is useful in automotive industry for designing car interior lining, safety belts and seat covers, but also for the printing of flags and banners, and outdoor and athletic wear, such as cycling jerseys and pants.

The examples which follow serve to illustrate the invention. In these examples the temperatures are in degrees Celsius and parts and percentages are by weight unless specified otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the litre. Example 1 :

0.70 parts by weight of a mixture of the yellow disperse dyes of formulae (301 ), (302) and (303) in equal parts,

1.00 part by weight of the orange disperse dye of formula (401 ),

1.10 parts by weight of a mixture of the red disperse dyes of formulae (501 ) and (502) in equal parts,

3.50 parts by weight of a mixture of the blue disperse dyes of formulae (601 ) and (602) in equal parts,

0.40 parts by weight of the navy disperse dye of formula (7),

0.60 parts by weight of the violet disperse dye of formula (9),

are stirred with

6.70 parts by weight of a mixture of a commercial non-ionic dispersing agent and commercially available ligninsulfonates, and the composition obtained is then milled in a wet mill to an average particle size of from 0.2 to 1.0 μΐη. Thereafter the ink, by addition with thorough stirring of

1.0 part by weight of a mixture of Surfynol^® 420 and Agnique^® CSO 35 containing 20% of Surfynol^® 420,

0.2 parts by weight of a commercial preservative,

30.0 parts by weight of a commercial humectant and

54.8 parts by weight of deionised water,

is adjusted to a dye content of 7.30% by weight based on the total weight of the ink. The composition obtained is micro-filtered and a stable ink is obtained which shows a good run- ability.

The ink is printed on a polyester fabric and on a polyester microfibre fabric (Alcantara) using an Inkjet printer operating by the drop-on-demand piezo technique. The prints are dried and fixed in superheated steam at 180°C for 8 minutes.

Deep black prints of a high colour strength having good all-round fastness properties, especially high temperature light fastness, are obtained. The high temperature light fastness of the polyester fabric and polyester microfibre fabric according to VDA 75202 is rated 4-5 and 3-4 (Grey Scale), respectively. Deep black prints of a high colour strength having good all-round fastness properties, especially high temperature light fastness, are likewise obtained if the dried print is fixed with hot air at 200°C for 1 minute.

Example 2:

Example 1 is repeated using 1.0 part by weight of a mixture of Surfynol^® 420 and Drehscofix³ CO 140 containing 20% of Surfynol^® 420 instead of 1.0 part by weight of a mixture of Surfynol^® 420 and Agnique^® CSO 35. A stable ink is likewise obtained which shows a good run-ability. Deep black prints of a high colour strength having good all-round fastness properties, especially high temperature light fastness, are obtained on a polyester fabric and on a polyester microfibre fabric (Alcantara).

Example 3:

Example 1 is repeated using 1.0 part by weight of a mixture of Surfynol^® 420 and Soprophor⁴ 3D33 containing 20% of Surfynol^® 420 instead of 1.0 part by weight of a mixture of Surfynol^® 420 and Agnique^® CSO 35. A stable ink is likewise obtained which shows a good run-ability. Deep black prints of a high colour strength having good all-round fastness properties, especially high temperature light fastness, are obtained on a polyester fabric and on a polyester microfibre fabric (Alcantara).

Claims

What is claimed is:

1. An aqueous ink comprising

(A) at least one disperse dye, and

(B) a surfactant system comprising a mixture of

(b1 ) at least one first surfactant of the formula

HO-B— C— C≡C— C— B— OH

^{C H}3 ^{C H}3 (1 ), and

(b2) at least one second surfactant selected from the group alkoxylated castor oil and tristyryl phenol alkoxylate of the formula

wherein

B and E are each independently of the others a radical of the formula -O-CH2-CH2-, -0-CH(CH₃)-CH₂- or -0-CH₂-CH(CH₃)-,

I is a number of from 1 to 40.

2. An aqueous ink according to claim 1 , wherein

Q₁ and Q₂ each independently of the other is CrC₆alkyl, which is branched or unbranched.

3. An aqueous ink according to either claim 1 or claim 2, wherein

B and E are each a radical of the formula -0-CH₂-CH₂-.

4. An aqueous ink according to any one of claims 1 to 3, wherein the sum of m+n is a number of from 1 to 20, and

5. An aqueous ink according to any one of claims 1 to 4, wherein I is a number of from 5 to 20.

6. An aqueous ink according to any one of claims 1 to 5, wherein the at least one disperse dye comprises

wherein

i is CrCi₂alkyl, or C₂-Ci₂alkyl interrupted by one or more oxygen atoms and/or -COO- groups, and

R₂, R3, R4 and R₅ each independently of the others is hydrogen, d-C₁₂alkyl, chlorine, bromine, hydroxy or amino;

wherein

R₆ is hydrogen, bromine, chlorine or cyano,

R₇ is trifluoromethyl, bromine or chlorine,

Rs is hydrogen, methyl or acetylamino, Rg and R10 each independently of the other is Ci-C4alkyl unsubstituted or substituted by cyano or by acyloxy, one of the C C₄alkyl radicals R₉ and R₁₀ is substituted by cyano or by acyloxy; and

wherein

one of the radicals R₁₄ and R₁₅ denotes hydrogen or CrC₆alkyl unsubstituted or substituted by hydroxy, C C₄acyloxy, C C₆alkoxy, CrC₄acyloxy-CrC₆alkoxy, or hydroxy-C C₆alkoxy, and the other one of the radicals R14 and R15 denotes d-Cealkyl unsubstituted or substituted by phenoxy-CrC₆alkoxy, or phenyl that is unsubstituted or substituted by one or more substituents from the group CrC₁₂alkyl, CrC₁₂alkoxy and trifluoromethyl.

7. An aqueous ink according to any one of claims 1 to 6, wherein the at least one disperse dye furthermore comprises

(a4) at least one dye of the formula

wherein

one of the radicals R₁₇ and R₁₈ denotes hydroxy and the other one of the radicals R₁₇ and R₁₈ denotes amino or nitro,

Rig is hydrogen or phenyl unsubstituted or substituted by one or more substituents from the group hydroxy and C C₆alkoxy, and R20 denotes hydrogen or phenyl that is unsubstituted or substituted by one or more substituents from the group hydroxy, halogen, d-Cealkoxy or CrC₆alkyl unsubstituted or substituted by hydroxy.

8. An aqueous ink according to any one of claims 1 to 7, wherein

R₁ is ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl or 3-isopropoxypropyl, and R₂, R3, R4 and R₅ are each hydrogen.

9. An aqueous ink according to any one of claims 1 to 8, wherein

R₁ is n-propyl, n-butyl, isobutyl or n-hexyl.

10. An aqueous ink according to any one of claims 1 to 9, wherein

R₆ is bromine or chlorine,

R₇ is trifluoromethyl or chlorine,

R₈ is hydrogen or acetylamino, and

R₉ and R10 is each cyanoethyl.

1 1 . An aqueous ink according to any one of claims 1 to 10, wherein the dyestuff component (a3) is at least one dye of formula

wherein

R11 is trifluoromethyl or cyano,

R12 and Ri3 each independently of the other represent hydrogen, fluoro, chloro, bromo, cyano or nitro,

one of the radicals R₁₄ and R₁₅ denotes hydrogen, 2-hydroxyethyl or the radical of formula -(CH2)2-0-(CH₂)2-OH, and the other one of the radicals R14 and R15 denotes the radical of formula -(CH₂)3-0-(CH₂)2-0-phenyl, or phenyl that is unsubstituted or substituted by one or more substituents from the group trifluoromethyl, n-propyl, n-butyl and n-butoxy.

12. An aqueous ink according to any one of claims 1 to 1 1 , wherein dyestuff component (a4) is at least one dye from the group of formulae

13. An aqueous ink according to any one of claims 1 to 12, which comprise 0.70 to 1.00% by weight of dyestuff component (a1 ),

0.85 to 1.15% by weight of dyestuff component (a2),

1.10 to 1.50% by weight of dyestuff component (a3) and

3.15 to 4.35% by weight of dyestuff component (a4),

based on the overall weight of the ink composition.

14. An ink-jet printing process for printing semi-synthetic or synthetic hydrophobic textile fibre materials, wherein the said fibre materials are printed with an aqueous ink according to claim 1.

15. An ink-jet printing process according to claim 14, wherein polyester fibre materials or fibre materials comprising blends of polyester with other fibres are printed.