US 2090890 A
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Patented Aug. 24, 1 93? UNITED STATES TEXTILE PRINTING Samuel Howard and Alec Worm'ald, Blackley,
Manchester, England, assignors to Imperial- Ohemical Industries Limited, a corporation of Great Britain No Drawing. Application February 11, 1935,
Serial No; 6,131. ary 19, 1934 9 Claims.
This invention relates to textile printing. More particularly, this invention deals with the printing of textile material, such as cotton fabric, with vat dyestuffs. By the term printing hereinafter wemean to embrace all processes, such as printing, padding, spraying, stencilling or otherwise applying color to fabric in areas of spe-- cial design.
It is an object of this invention -to provide a 10 novel process and reagents for producing resist styles, that .is areas where the fabric opposes the adsorption of color. Other and further important objects of this invention will appear as the description proceeds.
We have found that cotton fabric or other textile materials having an affinity for leuco-esters of vat dyestuffs will develop local resistance toward such dyestuffs if printed first with a composition comprising a salt of an organic compound as more fully defined below. This preprinting step is in general the same as the process known as resist printing, and the composition mentioned may be of the usual type used in such cases, comprising a gum adapted to cause adherence, water and the special assistants or resisting agents above referred to.
The novel efiect of this invention is that the resisting effect of the organic salts employed by us is greater than by the assistants generally 30 used heretofore, the resist-areas developing into a substantially clear white, exposing the original uncolored material.- Also, our novel assistants are successful in many cases where resist-effects have heretofore been impossible or difficult to 35 obtain. This effect is particularly brought out in the case of the sulfuric acid esters of leuco-vat dyestuffs of the anthraquinone series, known generically as the "-Soledons. These esters have great 'aflinity for cotton fabric and are on this 40 account difficult to resist to a clear white.
The novel assistants above referred to, and useful for this invention, are water-soluble salts of organic bases, or quaternary ammonium, phosphonium or sulfonium compounds, containing in their structure a saturated or unsaturated long-- In Great Britain Februthis respect, this group of assistants contrasts with ordinary soaps, such as sodium stearate,
palmitate or oleate, in which the organic radical is the anion, whilethe cation is inorganic.
More specifically, the assistants useful for our invention may be salts of primary, secondary or tertiary amines, quaternary ammonium compounds, salts of heterocyclic organic bases, or quaternary phosphonium or sulfonium compounds. The organic radical may contain an open chain of .at least Scarbon atoms, or it may contain the'benzyl or other aralkyl groups.
The following table and examples will further illustrate the types of compounds which we have found applicable for our purpose, but it should 'be understood that our invention is by no means limited to these specific illustrations. In the examples which follow, the parts mentioned are by weightz' Derivatives of ammonia:
Aniline hydrochloride Dimethyl-aniline-hydrochloride Dimethyl-benzyl-phenyl-ammonium chloride Tetramethyl-diamino-diphenyl-ketonimine Derivatives of heterocyclic bases:
Oleic acid ester of N-hydroxyethyl-pyridin ium chloride Cetyl ether of N-hydroxymethyl-pyridinium chloride Derivatives of sulfur:
. Cetyl-dimethyl-sulfonium methyl-sulfate Benzyl-cetyl-methyl-sulfonium methyl-sulfate Dodecyl-dimethyl-sulfonium bromide Benzyl-methyl-dodecyl-sulfonium chloride Benzyl-ethyl-decyl-sulfonium chloride Benzyl-methyl-dodecyl-sulfonium methylsulfate 9,090,890 Derivatives of phosphorus: Example II cetyLmmethyl phosphonium biomide Cotton cloth is printed with the following Dodecyl-trimethyl-phosphonium bromide paste: Parts Some of the above are novel compounds, and British gum (40% solution) 60 are described more fully and claimed in copend- Water 30 ing applications Serial Nos. 611,236, 28,013 and 47,470. Their general schemes of synthesis, however, may be illustrated briefly by the following examples.
Dimethyl-dicetyl-ammonium bromide may be prepared by reacting one equivalent of dimethylamine and two equivalents of cetyl bromide. Dimethylcetyl-sulphonium methyl-sulfate may be prepared by treating cetyl bromide with sodium hydrosulfide in alcohol, subjecting the mercaptan thus formed to an alkylation treatment with dimethyl-sulfate and caustic sodafland thereafter obtaining the salt by treatment with dimethylsulfate .alone. Benzylmethyldodecyl-sulfonium methyl-sulfate is obtained by treating the mercaptan derived from dodecyl bromide with a mixture of sodium ethoxide and benzyl chloride and finally treating the resulting product with dimethyl-sulfate.
Benzylcetylmethylsulfonium methyl-sulfate is madeby treating cetyl mercaptan with sodium in methanol and then heating with benzyl chloride; the resulting cetyl benzyl mercaptan is then heated with dimethyl sulfate. Dodecyldimethylsulfonium bromide is made by heating dodecylmethyl sulfide with methyl bromide until a completely water-soluble product is obtained;
dodecyl methyl sulfide is itself made by interacting equivalent quantities of dodecyl mercaptan and dimethyl sulfate in aqueous alkaline medium. Benzylmethyldodecylsulfonium chloride is made by heating dodecyl methyl-sulfide with benzyl chloride until a completely watersoluble compound is produced.
Cetyl-trimethyl-phosphonium bromide may be prepared by interacting trimethylphosphine and cetyl bromide: and dodecyltrimethylphosphonium bromide may similarly be made from dodecyl bromide and trimethylphosphine.
Ezample I Cotton cloth is printed with the renewing 0 paste:
I Parts British gum (40% solution) 65 Water 30 Benzylpyridinium chloride 5 The printed material is dried and then overprinted with the following paste:
Soledon jade green (sulfuric ester of leucodimethoxy-dlbenzanthrone; Color Index No. 1101) 500 paste 2.5 Water l 25 5 Neutral starch tragacanth thickening--- 70 vSodium nitrite (30% solution) 2.5
Parts 7 Dimethylbenzylphenylammonium chloride 10 100 The printed material is dried and overprinted with a paste consisting of Parts Soledon Brilliant Purple 2R (leuco ester of dichloro-isodibenzanthrone; Color Index No. 1104) v200 paste 5 Water 12 Diethylene glycol 8 Neutral starch tragacanth thickening Ammonium sulfocyanide (50% solution) 6 Sodium chlorate (10% solution) 8 Ammonium vanadate (1% solution) 1 Example IV Cotton cloth is printed with the following paste:
Parts British gum (40% solution) Water 30 Benzylpyridinium chloride 5 The printed material is dried and padded in a solution containing:
Parts Soledon orange 4R8 (leuco ester of dibromopyranthrone; Color Index No. 1098) paste--- 50 Water 1000 Sodium nitrite (30% solution) 25 The padded material is dried and developed -by passing at 60 C. through a bath containing 20 parts of sulfuric acid (168 Tw.) per 1000 parts of water, washed and soaped for 5 to 10 minutes at the boil.
Example V Cotton cloth is printed with the following paste:
Parts British gum (40% solution) 60 Water 35 Cetyltrimethylammonium bromide 5 The cloth is dried and overprinted with the following paste:
Parts Soledon jade green (6% solution) 5 Sodium nitrite 5 Neutral starch tragacanth thickening 60 Water 30 2,oao,sco 3 The neutral starch tragacanth thickening is made by dissolving 225 parts of wheat starch in 1500 parts of boiling water and mixing the. paste with 1000 parts of 8% gum tragacanth.
The cloth is then steamed for 5 minutes, passed through a 2% solution of sulfuric acid (168 Tw.) at' 60 c., rinsed in water, boiled in a l% soap solution for minutes, rinsed in water and dried. A clean white resist on a green ground is obtained.
The cloth is dried and padded for 5 seconds at 60 C., in a solution containing 7 parts of 9.10% aqueous paste of the sulfuric star of Caledon yellow G. (Color Index No. 1118), 5 parts of sodium nitrite, and 1000 parts of water.
' The cloth is squeezed, passed through a 2% solution of sulfuric acid (168 Tw.) for 2 minutes at 60 C., rinsed, boiled in a 1% s'oap solution for 10 minutes, rinsed' and dried. T
ExampleVII Cotton cloth is printed with the following aste: l'
British gumsolution) 60 Water 25 Dimethylcetylsulfonium /methyl-sulfate 15 4 The printed material is dried, and then overprinted with the following paste:
a Pal-tsv Soledon jade green XS paste 2.5 Water 25,
Neutral starclf tragacanth thickening '10 Sodium nitrite (30% solution) 2.5
The overprinted material is dried and developed by passing at 60 C. through a bathcontaining 20 parts of sulfuric acid (168 'rw.) per 1000 parts of water washedand soaped for 5 minutes at the boil. A white resist is obtained on a green e Example VIII Cotton cloth printed with the, resist paste, as
in Example vn, is driedand padded an the following solution:
' Parts Soledon yellow GS (leuco ester offlavahthrone; Color Index No. 1118) paste 3 Sodium nitri 5 5 Water 1000 The cloth is squeezed, then iieveloped and finished as in Example VII. Awhite resist 'is ob- 'tained on a yellow ground;
[Example IX Cotton is printed with the following paste:-
Parts British gum r 60 ter I 35 W8 Dodecyltriethylphosphonium bromide 5 The printed material is dried and padded in the following solutionzv Parts- S oledon jade green XS paste 20 Glycerine 20 5 Water r 1000 Gum ti'agacanth 50 Sodium nitrite (30% solution) 20 dried and treated as in Example VII.
Dodecyl triethylphosphonium bromide may be' prepared by reacting triethylphosphine with dodecyl bromldein ethereal solution at 80 C. to
It will'be understood that our invention is 15 susceptible of wide variation in practice without departing from the spirit of this invention.
. It will be further understood that we selected for the purpose of illustration leuco-esters of vat dyes merely because thesehave great afiinity for 20 cotton fabric and are therefore particularly difficult to' resist to a clear white. The effects of our novel assistants are therefore best brought out by the use of this typeof dyestufi. 'It is obvious, therefore, that good resistefiects may be 25 obtained also where the dyestufl does not have any superior affinity for the fabric, for instance, in coloringcotton with a mixture of a vat "dyestuff in ordinary quinone form and the usual reducing agents such as hydrosulflte, rongalite, 30
I We claim: 1. The-process of resisting cotton against coloration by leuco-esters of vat dyestuffs which have great affinity for cotton, which comprises apply- 35 ing to'the'same locally a printing gum compris- 7 ing a water-soluble organic salt of an inorganic acid chosen from the group consisting of organic ammonium compounds. organic phospho'nium compounds and organic sulfonium compounds,
each of which contains an organic radicle of at least 6 carbon atoms but no ionizable substituents which would impart to said radiclean anionic character. I t f 2. The process of producing colored designs upon'cotton fabric which comprises printing said fabric locally with a printing paste comprising a salt of an organic nitrogenous base and inorganic acid, the organic portion of said nitrogenous base being characterized by possessing at least 6 car-- 5 bon atoms and being free of anionic substituents then applying to said fabric a sulfuric acid ester of a leuco-anthraquinone vat color, and then developing the color and resist patterns.
' 3. The process of producing colored designs 55 upon cotton fabric'wh'ich comprises printing said fabric locally with a printing paste comprisinga salt of an inorganic acid and a quaternary organic heterocyclic nitrogenous-base free from anion-forming ionizable substituents-then apply- 3 ing to said fabric a sulfuric acid ester of a leuco- .anthrafiuinone vatdyestuff, developing the color pattern by hydrolysis and oxidation, and washing outthe resist pattern. a
4. The process of producing colored designs upon cotton: fabric which comprises printing said fabriclocally with a printing paste comprising a salt of an inorganic acid and tertiary organic sulfonium compound, then applying to said fabric a-sulfuric-acid esteroi' a 'leuco anthraquinone vat dyestuif, developing the color pattern by hydroly-- sis and oxidation, and washing out the resist pattern 5. The process of'producing colored designs upon cotton fabric which comprises printing said fabric locally with a printing paste comprising a salt of an inorganic acid and a quaternary or- 'ganic phosphonium compound, then applying to said fabric a sulfuric acid ester of a leuco-anthraquinone vat dyestuii', developing the color pattern by hydrolysis and oxidation, and washing out the resist pattern.
6. The process of producing white resists on cellulosic fabric under sulfuric esters of leuco vat dyestuffs which have a strong aflinity for cotton,
which comprises printing said fabric with a resist 20 which comprises printing said fabric with a resist paste containing a quaternary ammonium halide white resists against such leuco-esters of vat dyestuffs of the anthraquinone series which are dlill-' cult to resist by ordinary methods, which comprises printing said fabric with a resist paste containing dimethyl phenyl benzyl ammonium chloride, then applying to the fabric a leuco-ester of. a vat dyestuif, and developing the color.
9. The process of producing upon cotton fabric white resists against the sulfuric acid ester of leuco-dimethoxy-dibenzanthrone, which comprises printing said fabric with a resist paste containing dimethyl-pheny1-benzyL-ammonium chloride, then applying said color and developing the same upon the fiber.
SAMUEL HOWARD. ALEC WORMALD.