Method for printing fibrous textile materials according to...

Incremental printing of symbolic information – Ink jet – Fluid or fluid source handling means

Reexamination Certificate

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C347S101000, C347S096000

Reexamination Certificate

active

06443569

ABSTRACT:

The present invention relates to a method for printing fibrous textile materials according to the ink-jet printing technique.
Ink-jet printing processes have been used in the textile industry for some years. Such processes make it possible to dispense with the otherwise customary production of a printing screen, so that considerable savings can be made in terms of cost and time. Especially in the case of the production of pattern originals it is possible to respond to a change in requirements within a significantly shorter period of time.
Such ink-jet printing processes should especially have optimum characteristics from the standpoint of application technology. In this connection mention may be made of characteristics such as the viscosity, stability, surface-tension and conductivity of the inks used. Furthermore, higher demands are being made of the quality of the resulting prints, e.g. in respect of colour strength and fastness to wetting. Those demands are not met by the known processes in all characteristics, so that there is still a need for new processes for the ink-jet printing of textiles.
The invention relates to a process for printing fibrous textile materials according to the ink-jet printing technique, wherein the fibrous materials are printed with an aqueous ink comprising a pigment dye together with a water-dispersible or water-soluble pigment dye binder.
Suitable pigment dyes for the process according to the invention include both inorganic pigments, e.g. carbon black, titanium dioxide and iron oxides, and organic pigments, especially those of the phthalocyanine, anthraquinone, perinone, indigoid, thioindigoid, dioxazine, diketopyrrolopyrrole, isoindolinone, perylene, azo, quinacridone and metal complex series, for example metal complexes of azo, azomethine or methine dyes, and also classic azo dyes of the &bgr;-oxynaphthoic acid and acetoacetarylide series or metal salts of azo dyes. It is also possible to use mixtures of different organic pigments or mixtures of one or more inorganic pigments with one or more organic pigments. Examples of such pigment dyes are listed under “Pigments” in the Colour Index, 3rd edition (3rd revision 1987 inclusive Additions and Amendments up to No. 85). Pigment dyes of the monoazo, disazo, phthalocyanine and anthraquinone series and also inorganic pigment dyes, such as carbon black and iron oxides, are of special interest.
Especially preferred pigment dyes are dyes of formula
wherein
R
52
is hydrogen, halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, nitro or cyano,
R
53
is hydrogen, halogen, nitro or cyano,
R
54
is hydrogen, halogen or phenylaminocarbonyl,
R
55
is hydrogen or hydroxy, and
R
56
is hydrogen or a radical of formula
wherein
R
57
is hydrogen, C
1
-C
4
alkyl or C
1
-C
4
alkoxy,
R
58
is hydrogen, C
1
-C
4
alkoxy or halogen, and
R
59
is hydrogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or halogen,
and dyes of formula
wherein
R
60
and R
61
are each independently of the other C
1
-C
4
alkyl and R
62
and R
63
are halogen,
and dyes of formula
wherein the rings A, B, D and E are unsubstituted or mono- or poly-substituted by halogen, and dyes of formula
wherein
R
64
is C
1
-C
4
alkyl,
R
65
is hydrogen, halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, nitro or cyano,
R
66
is hydrogen, halogen, nitro or cyano,
R
67
is hydrogen, halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, nitro or cyano,
and dyes of formula
wherein the rings A′ and B′ are unsubstituted or mono- or poly-substituted by halogen, and dyes of formula
wherein
(R
68
)
0-2
and (R
68
′)
0-2
each independently of the other denote from 0 to 2 substituents selected from the group halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, nitro and cyano, and
K
1
and K
2
are each independently of the other a radical of formula
wherein
(R
69
)
0-3
and (R
69
′)
0-3
each independently of the other denote from 0 to 3 substituents selected from the group halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, nitro and cyano, especially halogen, C
1
-C
4
alkyl and C
1
-C
4
alkoxy.
Inorganic pigment dyes, such as carbon black and iron oxides, are also of interest.
Of special interest as pigment dyes are the dyes of formulae
Further interesting pigment dyes are C.I. Pigment Black 7, C.I. Pigment Red 101, C.I. Pigment Yellow 17, C.I. Pigment Yellow 34, C.I. Pigment Yellow 83 and C.I. Pigment Yellow 128.
In the process according to the invention it is especially preferred to use as pigment dyes those of formulae (7e) and (7g) and also C.I. Pigment Yellow 83 and C.I. Pigment Black 7.
The mentioned pigment dyes are known or can be obtained analogously to known preparation procedures, such as diazotisation, coupling, addition and condensation reactions.
Examples of binders that come into consideration include pigment dye binders based on the polymerisation product of at least one of the components acrylic acid; other acrylic monomers, e.g. acrylic acid esters; and urethane. Preference is given to pigment dye binders based on the polymerisation product of at least one of the components acrylic acid and urethane. Of special importance are pigment dye binders based on the polymerisation product of acrylic acid; or urethane; or urethane and acrylic acid. Of special interest are mixtures of pigment dye binders wherein one component of the mixture is based on the polymerisation product of acrylic acid and another component of the mixture is based on the polymerisation product of acrylic acid and urethane. The pigment dye binders are water-dispersible or, preferably, water-soluble. Examples that may be mentioned include Carboset® 531 and Sancure® AU4010 from BFGoodrich.
In a very special embodiment of the process according to the invention, the polymerisates that come into consideration as binders do not contain sulfo or sulfato groups.
The inks preferably have a total content of dyes of from 1 to 35% by weight, especially from 1 to 30% by weight and more especially from 1 to 20% by weight, based on the total weight of the ink. As a lower limit, a limit of 2.5% by weight, especially 5% by weight and more especially 10% by weight, is preferred.
The pigment dye binder is present in the ink preferably in an amount of from 2 to 30% by weight, especially in an amount of from 5 to 20% by weight.
Preferred for the process according to the invention are those inks which have a viscosity of from 1 to 40 mPa·s (milliPascal·seconds), especially from 1 to 20 mPa·s and more especially from 1 to 10 mPa·s. Inks having a viscosity of from 2 to 5 mPa·s are of special importance. Also of importance are inks having a viscosity of from 10 to 30 mPa·s.
The inks may comprise thickeners of natural or synthetic origin, inter alia for adjusting the viscosity.
Examples of thickeners that may be mentioned include commercially available alginate thickeners, starch ethers and locust bean flour ethers. Cellulose ethers may also be mentioned.
Examples of cellulose ethers that come into consideration include methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropyl cellulose and hydroxypropyl methylcellulose. Carboxymethylcellulose and hydroxypropyl methylcellulose are preferred. The cellulose ethers are preferably water-soluble. As synthetic thickeners there may also be mentioned, for example, those based on poly(meth)acrylic acids or poly(meth)acrylamides. As alginates there come into consideration especially alkali alginates and preferably sodium alginate. The thickeners are used in the ink usually in an amount of from 0.01 to 2% by weight, especially from 0.01 to 1% by weight and more especially from 0.01 to 0.5% by weight, based on the total weight of the ink. Such thickeners enable the ink to be adjusted to a specific viscosity.
As further additives, the inks may comprise surfactants, redispersants or humectants.
Suitable surfactants include commercially available anionic and non-ionic surfactants. An example of a redispersant is betaine.
The pigment dyes are advantageously used in dispersed form.
For the preparation of the dye dispersions it is possible

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