US2003960A - Printing - Google Patents

Description

Patented June 4, 1935 UNITED STATES 2,003,960 PATIENT OFFICE PRINTING Ronald Tonkin and James Stevenson Wilson, Earls Road, Grangemouth, Scotland, assignors to Imperial Chemical Industries Limited,v a corporation, of Great Britain.

No Drawing. Application June 8, 1932, Serial No. 616,098. In Great Britain June 16, 1931 20 Claims.

. reducing agents and assistants, and then aged bypassing through a steaming chamber, improper and uneven fixation of the color present in the printing paste is liable to be encountered.

It is an object of the present invention to avoid or reduce the foregoing disadvantages. Further objects are the provision of new printing assistants, new printing'pastes, and a new and improved'process of printing. A still further object is the production and use of highly efficient vat color printing pastes. Other objects will appear hereinafter.

These objects are accomplished according to this invention by incorporating or including with printing pastes quaternary base compounds of the following general formula:

Example I A printing paste is prepared according to the following recipe:

. Parts 3 3'-dichloro-dianthraquinone 1:2:2':1'-dihydroazine, single strength paste British gum thickening 9 Glycerine 2 Rongalite C- t g 1.8 Potash 3.2 Choline chloride 4 Cotton cloth is printed with the foregoing paste in the usual way, that is, by passing the cloth to be printed under some tension and pressure over an intaglio metal roll, the engraving of which is filled withthe printing paste.

After leaving the printing machine the printed cloth is passed into a drier whereby the printing paste is dried on the cloth in its proper place and the dye is prevented from spreading to other portions of the fabric. In order" to complete the printing, the cloth, after leaving the drier, is

passed into a steam ager for a period of a few minutes during which time the vat color undergoes reduction and passes to the fiber. The fabric is then subjected to oxidizing conditions which may include passing it into a steeping bath, usually of water or water containing an oxidizing agent. Any excess color is washed off in a soap solution with which the textile material is treated following the steeping. The printed material possesses stronger and brighter shades than are obtained without choline-chloride.

Example II Instead of the dye 3:3-dichloro-dianthraquinone-1:2:2':1'-dihydr0azine, Caledonv brown RS (4:5' di(benzoy1amino) 1:1'-dianthraquinonyl carbazole) paste is used in the printing paste of Example I with good results.

Example III A printing paste is prepared according to the followingrecipe:

Parts 3 3'-dichloro-dianthraquinone 1:2:2' 1'-dihydroazine, .single strength paste 5 British gum thickening 11 Glycer I 2 Rongalite C 1.8 Potash 3.2 .Cho1inechloride I- 2 Cotton cloth is printed with this paste, dried, and steamed in the ager. The printed material possesses stronger and brighter shades than are obtained without choline chloride.

Example I? The 3:3dichloro-diahthraxiuinone-1:2:2' 1'- dihydroazine of Examples I and III is replaced by 4 4 -dimethyl-6 :6 dichlorthioindigd paste with very desirable results.

The new printing assistants preferably employed in accordance with the invention are due.- ternary base compounds as already defined which are non-volatile or substantially non-volatile under the conditions of'operation and which are strong bases or salts of strong bases and which are hygroscopic or deliquescent. The results obtained with.- choline chloride in particular have been very highly advantageous. This compound may be represented by the following formula;

CH3 CHaCHrOH CHa-N CH; Cl

- As further examples of the new printing assist- H: CH!

Hydroxyethyl trimethyl ammonium suifite o'momon cm omomon CHaN--O-SONCH:

g (EH:

13H: CH: 7 Hydroxyethyl trimethyl ammonium sulfate HO.CH2.0H: CHIC6HB CHa-N-C'l H: Benzyldimethyl hydroxyethyi ammonium chloride CHaCeHt HO.OH:.OH2-N-OH C s CH3 Benzyldimethyi hydroxyethyl ammonium hydroxide HO.CH:.CH1 CHzCtHs HO.CHa.OHi- H0.0Hz.CH: Cl

Benzyltrihydroxyethyl ammonium chloride H0.0H:.0H: OHZOIHI HO.GH:.OH:NOH

0113 Benzyl di(hydroxyethyl)methyl ammonium hydroxide HO-OHl-CH] CH; CH3- 0H,. 0.80;.Na Hydroxyethyl trimethyl ammonium sodium sulfate HO.CH:.CH| CH3 CHa-N ona o.so,.o,m Hydroxyethyl trimethyl ammonium benzenesulfonate H0.CH:.OH9 0H1 CHQ;N\ CH; 0.80:.H Hydroxyethyl trimethyl ammonium acid-sulfate It will be obseryed that the compounds falling within the invention may be classified in various ways. Thus, those of Formulae (4), .(9) and (11) are members of a group represented by the gen:

eral formula in which X is SO4 R (where R is hydrogen, metal, or an organic radical, including the radical Ilia as already defined) Quarternary base compounds containing other stable acid residues such as, for example, phosphates may be classified similarly. I

In practicing the invention, especially desirable results have been obtained in printing vatcolors of the indanthrone series, particularly 3:3'-dichloro dianthraquinone-l :2: 1' :2'-dihydroazine.

As examples of other printing colors may be mentioned: Caledon blue RC, 6:6 diethoxy thioindigo, 7:7, dimethyl 5:5 dichlorthioindigo, 5:6:5':6' tetrabromindigo, bisbeta naphthionaphthene indigo and 4:4 dichlor- 5:5' dibromindigo.

As is well known a composition of printing paste may vary widely with different dyes and manufacturers but, in the case of vat colors,

usually consists of a mixture 01 an unreduced vat dye, a strong reducing agent such as, sodium hydrosulphite or Rongalite, an alkali and a thickening agent. The thickening agent is usually a gum (for instance British gum), starch or both. Printing paste is usually prepared bymixing a dye paste or pastes with'the other ingredients enumerated, said other ingredients being in the form of a gummy mixture generally called a printing gum. The dye pastes are essentially finely divided suspensions of the dye with or without a dispersing agent. Printing assistants may be added to the dye paste or to the printing gum or the printing paste as desired.

The amount of printing assistant may vary within relatively wide limits but may ordinarily be varied directly with the amount of dye. Empirical tests can usually be made to determine the optimum amount of printing assistant for any given dye. Very satisfactory results are obtained-with proportions of printing assistant described in the examples but greater or lesser amounts may be employed if desired.

The process of the invention gives particularly valuable results with regard to fullness and brightness of shade when the sub-stratum upon which the color is printed is mercerized cotton. Good results are also obtained in printing other cotton materials and, in general, materials which may be printed with vat colors including viscose rayon and othr fibers, fabrics and yarns of vegetable origin.

While the invention is not limited to any theory, inasmuch as the quarternary bases employed as printing assistants are, in general, very deliquescent substances it appears probable that this property of deliquesence ispartly or wholly responsible for the improved results which are obtained by their use. .It may be that their presence assists in the absorption 01 water either before or during the steaming operation, by which means the conditions requisite for the proper fixation of the color are attained. They may also,

in some cases, exert a solvent action on the color. Most deliquescent inorganic salts are incompatible'with the alkaline mixtures used in printing, especially with vat colors, being decomposed to give difiicultly soluble hydroxides, oxides or ants is such that by their use greatly improved prints may be obtained with dyes which are ordinarily poor printing colors such as, for example, 3 3-dichloro-dianthraquinone 1:2:2' :1-dihydroazine.

As many apparent'and widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that we do not limit ourselves to the foregoing examples or description except as indicated in the following claims.

We claim:

1. Vat dye pastes comprising a water-insoluble vat dye and a quaternary base compound of the general formula where R1, Ra, R: and R4 are the same or different alkyl or aralkyl groups, one at least of which is an alkyl group containing a hydroxy group, and where X represents OH or an acid residue.

2. Vat dye textile printing pastes comprising a water-insoluble vat dye and choline or a salt thereof. r

"-3. Vat dy e printing pastes comprising a waterinsoluble vat dye and a water-soluble quaternary base compound of the general formula where R1, Ra, R3 and R4 are the same or different alkyl groups, one at least of which contains a hydroxy group, and where X represents OH or an acid residue.

4. Vat dye printing pastes comprising a waterinsoluble vat dye and a water-soluble quaternary base compound of the general formula Ill: X-N-Rz where R1, Ra, R: and R4 are the same or diiferen alkyl or aralkyl groups, one at least of which is an alkyl group containing a hydroxy group, and where X represents an inorganic acid residue.

5. A vat dye paste comprising a water-insoluble vat. dye and choline chloride.

'6. Printing pastes comprising. an anthraquinone vat dye and a water-soluble quaternary base compound of the general formula I'M 1 X-N-lt:

where R1, Ra, R: and Rare the same or different alkyl or aralkyl groups, one at least of which is an alkyl group containing a hydroxy group and where X represents -OH or an 'acid residue.

- '1. A process of printing textiles comprising adding to a paste containing a vat dye and other customary ingredients a water-soluble quaternary base compound of the general formula B" X--I|-I'R:

. where R1, R2, R2, and Ra are the same or different alkyl or aralkyl groups, one at least of which is an" alkyl group containing where x represents --OH or an acid residue and a hydroxy group and thereafter using the compounded paste in prlntclaim 7 wherein the paste contains a vat dye and choline or a salt thereof. r

9. A process of printing textiles as claimed in claim '7 wherein the dyestuif is 3'z3'z-dichlorodianthraquinone-1:2:2':1'-dihydroazine.

".10. A process of printing textiles as claimed in claim 7 wherein the dye is a chloro dianthraquinone-1:2:2':1'-dihydroazine.

11. A process of printing textiles as claimed in claim? wherein thepaste contains a chloro d1- anthroquinone-l :2 :2 :1--dihydroazine and choline chloride.

12. A dye paste of a. halogenated dianthraquinone-1:2:2' :1'-dihydroazine containing as an ingredient choline chloride.

13. A dye paste of a chloro dianthraquinonel:2:2:1'-dihydroazine containing as an ingredi ent choline chloride.

14. A dye paste of 3:3-dichloro-dianthraquinone-1:2:2:1-dihydroazine containing as an ingredient choline chloride.

15. A thioindigoid dye paste containing as an ingredient choline chloride.

16. A dye paste of 4:4'-dimethyl-6:6- -dichlorthioindigo containing as an ingredient choline chloride.

1'7. A dye paste of a di(benzoylamino) -l:1'-dianthraquinonyl carbazole containing as an ingredient choline chloride.

18. A dye paste comprising a water insoluble vat dye and a water-soluble quaternary base compound of the general formula:

where R1, Ra, R: and R4 are the same or different alkyl or aralkyl groups, one at least of which is an alkyl group'containing a hydroxy group, and where X represents OH or an acid residue.

20. The process of printing vat dyes which I comprises applying to the fiber a printing paste comprising the vat dye, an alkali, a reducing agent suitable for printing, a gum thickening agent, and a quaternary base compound of the general formula:

t R: t wherein R1, Ra, R: and R4 are the same or diflerent alkyl or aralkyl groups, one at least of which is an alkyl group containing a hydroxy rou and wherex represents OH or an acid residue, and thereafter developing the print.

RONALD 'I'ONKIN.

JAMES STEVENSON wit-son. v i