US2999731A

US2999731A - Dyeing of normal wool

Info

Publication number: US2999731A
Application number: US760874A
Authority: US
Inventors: Harding Arthur Jacob Immins
Original assignee: Woodlyn Corp
Current assignee: Woodlyn Corp
Priority date: 1958-09-15
Filing date: 1958-09-15
Publication date: 1961-09-12
Anticipated expiration: 1978-09-12

Description

N Drawing. Filed Sept. 15, 1958, Ser. No. 760,874 29 Claims. (Cl. 8-64) This invention relates to an improved dyeing process. It should be understood that the term dyeing as used herein includes printing fabrics using dyestuffs.

In the textile and hosiery industry an effect known as the ingrain or fleck effect has been produced by blending White wool with dyed wool in varying proportions in the spinning process to form yarn whereby a contrasting or fleck effect is produced in the yarn and knitted and Woven articles produced from the yarn. A similar effect known as the melange effect can be produced by blending wool of two or more colours in the spinning process. Similar effects can also be produced using mixtures of chlorinated and unchlorinated wools or resisttreated Wool and normal wool or chlorinated Wool and resist-treated wool.

In producing either of these effects some of the fibres may be printed in the slubbing before the spinning.

It is an object of the present invention to produce ingrain and melange effects from a single type of pure unchlorinated wool without the use of different coloured wools in the production of the yarn and without the necessity of using mixed chlorinated and unchlorinated wool or resist-treated wool and normal wool or chlorinated wool and resist-treated wool, or indeed without the use of any mixture of wools being necessary.

It is a further object of this invention to produce a dyed wool which is softer, has a better handle, better wearing qualities and a lower heat conductivity than the same Wool before dyeing or the same wool when dyed by conventional processes.

It is known that wool protein contains a number of amino acid residues which may be classified as follows:

groups, namely,

It has been discovered according to this invention that if the amino acids whose residues are found in wool are treated with certain substances under appropriate conditions of acidity, some of the amino acids are rendered wholly or partly resistant to dyeing with dyestuffs which normally dye wool.

According to the process of the present invention for non-uniformly dyeing or printing a single type of pure unchlorinated wool, the wool is treated with an aqueous solution or paste containing:

(a) A condensation product which renders some of the amino acids present in wool at least partially resistant to dyeing with dyestuffs which normally dye wool and which is a condensation product of an aldehyde, particularly formaldehyde and an aromatic sulphuric acid or a Water-soluble salt of such condensation product;

(b) A water-soluble organic aliphatic acid which is non- R atent assent Patented Sept. 12, 196i ice the said aqueous solutions or paste having an initial pH of between 2.8 and 4.9 preferably between 3.4 and 4.5.

Examples of the component (a) are: Condensation products of the general formula where R is an aryl radical which contains at least one sulphonic acid group and may contain one or more amino, hydroxyl, nitro, chlorine or thiol substituents and n is an integer, preferably 1 or 2 Specific examples of the compounds are dinaphthylmethane disulphonic acids, diphenylmethane disulphonic acids, dicresylmethane disulphonic acids, sodium dicresylmethane disulphonates, dixylylmethane disulphonic acids, diaminonaphthylmethane disulphonic acids, dichloronaphthylmethane disulphonic acids, dinitronaphthylmethane disulphonic acids and dithionaphthylmethane disulphonic acids.

It will be understood that the condensation products I may be made in situ and if dwired a sulphite or bisulphite may be present during the condensation.

Examples of sulphonic acids which may be used to form the condensation products are: mono-, di and trisulphonic acids or aromatic hydrocarbons, including alkylated aromatic hydrocarbons, such as naphthalene-1- sulphonic acid, naphthalene-2.7-disulphonic acid and naphthalene-Z-sulphonic acid; mono-, diand tri-sul phonic acids of monohyd-ric, dihydric and trihydric phenols, including alkyl substituted phenols.

It will he understood that mixtures of more than one of the above substances may be used, and it will also be understood that the sulphonic acids of the aromatic hydrocarbons used to form thecondensation products may contain more than one nucleus. Thus, for example, they may be derived from benzene, naphthalene, anthracene, diphenyl and dinaphthyl.

Substances which are of particular importance are condensation products of formaldehyde with mono, diand tri-sulphonic acids of aromatic hydrocarbons or phenols, especially diphenylmethane disulphonic acids, the condensation product of a cresol sulphonic acid with formaldehyde, or the condensation product of a naphthalene sulphonic acid with formaldehyde, particularly dinaphthylmethane di-sulphonic acids.

The dyestuffs employed may be selected from the classes of acid, neutral, direct, preametallised, chrome, and phosphorescent dyestuffs or, indeed, any dyestutf which Will dye wool, provided that it contains at least two sulphonic acid groups in the molecule.

Depending upon the nature of the component (a) the lower limit of the compounds employed may be between 0.000 0l% and 0.000025%, calculated on the weight of the liquor. Furthermore, as indicated above, the bath or paste containing the component (a) must have an initial pH between 2.8 and 4.9. During the treatment the pH will increase owing to adsolption of acid on the wool fibre.

Glaubers salt, Epsom salts, potassium chloride, sodium chloride, and/or Wetting agents may also be added to facilitate the process of the invention.

Furthermore, if desired, the Wool may be pretreated with an aqueous solution of sulphuric acid provided that it is washed before being heated by the process of the 0 present invention.

According to a modification of the invention the component (c), i.e., the dyestuif or the components (b) and (c) are applied to the wool after it has been treated with an equeous solution or paste containing the components (a) and (b) or the component (a) as the case may be.

According to a further modification the wool may first be treated with component (b) then with component (a), followed by component or the wool may be treated with component (b) and then with components (a) and (0) together. 7 i

If desired, the wool may be pre-treated with formaldehyde either before or during the treatment with compo: nent (a).

The melange effect can be produced by using two or more dyestuffs, some of which may be free from sulphonic acid groups or contain only one sulphonic acid group in the molecule.

If a mixture of a dyestuif with no sulphonic acid groups and a dyestulf with two or more sulphonic acid groups is employed, the dyestuff with no sulphonic acid groups dyes the Whole of the wool material whilst the dyestufif with two or more sulphonic acid groups dyes the wool material in darker flecks on a lighter ground, thereby giving a two-colour effect.

If a mixture of a dyestuif with one sulphonic acid group and a dyestutf with two or more sulphonic acid groups is employed, the dyestuff with two or more sulphonic acid groups dyes the wool material in darker flecks on a lighter ground, whilst the dyestutf with one sulphom'c acid group dyes the lighter part of the wool material and slightly stains the darker fleck part, thus giving two or more contrasting colours. v

If all the dyestuff employed contains two or more sulphonic acid groups, an in-grain or fleck effect is obtained which may be varied from a nearly solid through a tonein-tone to a fleck efiect on a practically white ground.

' If wool plated on cotton is employed then the wool can be dyed to give the effects of the present invention and the cotton can be dyed either in tone or in contrast. if a wool which is blended with cotton in the yarn is employed an ingrain effect can be dyed on the wool and the cotton can be dyed separately, or the wool may be dyed by the two-colour melange method of the present invention and the cotton dyed separately.

fWool dyed by the process of the present invention may be after-treated by a shrink-resist process.

The process of the present invention may be applied to wool yarn or to knitted or Woven wool fabrics or articles, and also to yarn or fabrics or articles containing wool and in admixture with other non-wool fibres such as Ardil, Terylene, cotton, nylon, rayon, casein fibre, acrylic fibres, cellulose acetate and fibro. Among the articles which may be treated according to the present invention are underwear, or outer-ewear garments, hose, half-hose, quarter-hose, three-quarter-hose, socks and stockings, felts, hats, ties, furnishing fabrics, upholstery for motor cars, gloves, scarves, wool curtains, rug and carpet wool, rabbit wool and slubbing.

Townend in The, Journal of the Society of Dyers and Colourists 61 1945 144-149, describes a process for the two colour dyeing of all wool materials. Although Townend uses dyestuffs containing two or more sulphonic acid groups in the molecule such as naphthalene Scarlet 4R8 (Colour Index No. 185) and Solway Blue BNS in conjunction with Lissatan Acwhich is a condensation product such as may be used according to the present invention Townends process is quite different from that of the present invention, since his process involves the use of a mixture of chlorinated and unchlorinated wool. The chlorinated wool takes up the dyestuif preferentially. Further, his process involves the use of sulphuric acid in such quantities and would produce a liquid having an initial pH of less than 2.8. Finally, the process of the present invention produces a dyed wool which is softer, has a better handle, better wearing qualities and lower heat conductivity than the same wool treated by Townends process even ifthe latter is modified by proceeding in the absence of chlorinated wool.

The following examples illustrate how the process of the invention may be carried into effect:

(1) 2.27 kgms. of previously secured white wool halfhose were dyed at the boil in a liquor having a pH of 3.2 and consisting of 90.6 litres of water containing *113 gms. (5% calculated on the weight of the goods) of Erional NW (a condensation product of a cresol sulphonic acid with formaldehyde, manufactured by The Geigy Colour Co., Ltd), 113.2 cos. of acetic acid and 20.4 gms. of Omega Chrome Navy Blue 4 BL 'Extra (a mixture based on Carmoisine LS (Colour Index No. 180)) (manufactured by 'Sandoz Products, Ltd.) and 2.04 gms. of Chromosol Yellow GD (manufactured by Sandoz Products, Ltd.) for 30 minutes whereafter 22.4 gms. of sodium bichromate were added and the dyeing continued for 30 minutes.

The dyed half-hose were grey in shade and showed a fleck effect similar to that obtained by knitting half-hose from ingrain yarn.

(2) 80 gms. of white Wool half-hose were dyed by entering them into a boiling liquor having a pH of 3.4 and consisting of 2500 cos. of water having dissolved therein 2 gms. of Solochrome Red BS 0.4 gm. of Solochrome Cyanine R 200% (both made by Imperial Chemical Industries Ltd.) and 3.3 gms. of Erional NW, and 3.5 gms. of 80% acetic acid. Boiling was continued for 25 minutes and 1.5 gms. of sodium bichromate were added and the dyeing continued for a further 25 minutes. The dyed half-hose were a wine colour fleck effect.

(3) 35 gms. of white wool half-hose were dyed by entering them into a boiling liquor having a pH of 3.4 and consisting of 1500 cos. of Water having dissolved therein 1.5 cos. of 80% acetic acid, 2 gms. of Lissatan AC (:1 25% solution of naphthalene-formaldehyde sulphonic acid manufactured by Imperial Chemical Industries, Ltd), 0.2 gm. of Soloch-rorne Blue PB (Colour Index No. 179), 0.02 gm. of Solochrorne Red BS 125% and 0.05 gm. of Solochrome Yellow G (all the dyestuffs mentioned in this example were manufactured by Imperial Chemical Industries, Ltd.) The boiling was continued for 25 minutes and then 0.1 gm. of sodium biohromate was added and the boiling continued for a further 25 minutes. The dyed half-hose showed a violet and yellow melange effect.

(4) 38 gms. of white wool half-hose were dyed by entering them into a boiling liquor having a pH of 3.7 and and consisting of 1500 cos. of water having dissolved therein 1.5 gms. of 80% acetic acid, 4 gms. of Lissatan F (a dinaphthylmethane disulphonic acid manufactured by Imperial Chemical Industries, Ltd), 0.2 gm. of Solochrorue Cyanine RS 200%, 0.2 gm. of Solochrome Yellow G and 0.2 gm. of Alizarine Red AS which is similar to the dyestuif described in Colour Index No. 1034 (manufactured by Imperial Chemical Industries, Ltd). The boiling was continued for 25 minutes and then 0.3 gm. of sodium bichromate was added and the dyeing continued for a furtheir-25 minutes. The dyed half hose showed a reddishpurple and yellow contrast melange efiect.

(5) 80 gms. of white wool half-hose were dyed by entering them into a boiling liquor having a pH of 3.2 and consisting of 2400 cos. of water having dissolved therein 4 gms. of the aforesaid Erional NW, 4 gms. of 80% acetic acid and 0.5 gm. of Neolan Red BRE (manufactured by the Clayton Aniline Co. ltd). The dyeing was carried out for 45 minutes and. a red fleck effect was produced.

(6) 10 gms. of white wool sock were dyed by entering the wool sock into a boiling, liquor having a pH of 3.2 and consisting of 250 ccs. of water having dissolved therein 12 cos. of a 2% aqueous Erional NW solution, 2 ccs. of 8% formic acid, 0.0092 gm. of Coomassie Acid Blue RL 150%, 0.0036 gm. of Solochrome Red B 125% and 010054 gm. of Solochrorne Yellow Y 125% (Colour Index No. 1-97). Boiling was continued for 30 minutes and then 0.0045 gm. of potassium bichromate was added and the boiling continued for a further 30 minutes. A grcywhite fleck effect was obtained;

(7) gms. of whitewool sock were dyed by entering the wool sock into a boiling liquor having a pH of 3.2 and consisting of 300 ccs. of Water having dissolved therein 2 ccs. of a 10% Basyntan UW solution (Basyntan UW is made by Messrs. Bush, Beach and Gent, Ltd. and is 8. formaldehyde condensation product of sulphonated higher hydrocarbons, mainly retenes), 5 ccs. of an 8%acetic acid solution, 0.0093 gm. of Coomassie Acid Blue RL 150%, 0.0036 gm. of Solochrome Red B 125% and 0.0054 gm. of Solochrome Yellow Y 125%. The boiling was continued for 30 minutes and then 0.4 cc. of a 2% sodium bichromate solution was added and the boiling continued for a further 30 minutes. A grey fleck effect was obtained.

(8) (a) 46 gms. of white wool half-hose were boiled for minutes in a liquor having a pH of 3.2 and con sisting of 1250 ccs. of water containing 2.5 gms. of formaldehyde, 2.5 gms. of 80% acetic acid and 1.5 gms. of Lissatan F. The half-hose was then washed in water containing 12 ccs. of a 0.66% solution of sodium sesquicarbonate to neutralise the acid.

(b) The half-hose was then dyed in a boiling liquor having a pH of 3.2 and containing 16 cos. of 8% acetic acid, 56 ccs. of a dye solution containing 17 ccs. of a 2% solution of Coomassie Acid Blue RL 150%, 6.5 ccs. of a 2% solution of Solochrome Red B 125% and 1 cc. of a 2% solution of Solochrome Yellow Y 125%, made up to 80 ccs. with water. The boiling was continued for 30 minutes, 1.6 ccs. of a 1% sodium bichromate solution were added and the boiling continued for a further 30 minutes. A mid-grey fleck effect was obtained.

(9) 46 gms. of white wool half-hose were treated as described in Example 8 (a). After washing with water 23 gms. of the half-hose were treated for 15 minutes at a temperature of between 38 C. and 49 C. with 15 ccs. of 10 volume hydrogen peroxide solution.

The half-hose were washed with water and 6 ccs. of a 0.66% solution of sodium sesquicarbonate was added to the half-hose in 650 ccs. of water. The half-hose Were dyed by entering into a boiling liquor having a pH of 3.2 and consisting of 650 ccs. of Water containing 28 ccs. of the dye solution mentioned in Example 8(b). The boiling was continued for 30 minutes and then 8 ccs. of a 1% sodium bichromate solution was added and the boiling continued for a further 30 minutes. A dark grey fleck effect was obtained.

(10) 10 gms. of white wool sock were dyed by entering the wool sock into a boiling liquor having a pH of 3.2 and consisting of 300 ccs. of water having dissolved therein 0.5 gm. of 80% acetic acid, 0.084 gm. of Coomassie Acid Blue RL 150%, 0.032 gm. of Solochrome Red B 125%, 0.05 gm. of Solochrome Yellow Y 125% and 0.125 gm. of Lissatan F and 0.125 gm. of Lissatan AC. The boiling was continued for 30 minutes and then 0.04 gm. of sodium bichromate was added and the boiling continued for a further 30 minutes. A very striking grey fleck effect was obtained.

(11) 455 gms. of white wool half-hose were dyed by entering the half-hose into a stainless steel overhead paddle machine containing a liquor having a pH of 2.8 and consisting of 22 litres of boiling water having dissolved therein 54 ccs. of 80% acetic acid, 27 ccs. of 80% formic acid, 29.7 gms. of Erional NW, 4.55 gins. of Neolan Blue 2R, 3.1 gms. of Neolan Red BRE and 2.6 gms. of Neolan Yellow 8GB (all the dyestuffs are manufactured by the Clayton Aniline Co. Ltd). The boiling was continued for 60 minutes and a tone-in-tone grey fleck effect was obtained.

(12) 6.35 kgrns. of white wool half-hose were dyed by entering the half-hose into a stainless steel overhead paddle machine containing a liquor having a pH of 3.3 and consisting of 155 litres of boiling Water having dissolved therein 14.96 gms. of Solochrome Red B 125%, 22.44 gms. of Solochrome Yellow Y 125% and 61.7 gms. of Coomassie Acid Blue RL 150%, 281 ccs. of 80% acetic acid and 140 gms. of Erional NW. The boiling was continued for 30 minutes. 28 gms. of sodium bichromate were then added and the boiling continued for a further 30 minutes. A good grey ingrain effect was obtained.

(13) 240 gms. of white wool sock were dyed by entering the wool sock into a boiling solution having a pH of 3.0 and consisting of 22.73 litres of water having dissolved therein 20 gms. of 80% acetic acid and 40 gms. of Erional NW and 0.5 gm. of Erio fast Red 2 BLS (manufactured by The Geigy Colour Co., Ltd) The boiling was continued for 60 minutes. A pink fleck effect was obtained.

(14) 12.23 kgrns. of white wool half-hose were dyed by entering the half-hose into an overhead Longclose paddle machine containing a liquor having a pH of 3.0 and consisting of 761 litres of boiling water having dissolved therein 1064 ccs. of 80% acetic acid, 212 gms. of Erional NW, 36 gms. of Solochrome Red B 125%, 54 gms. of Solochrome Yellow Y 125% and 108 gms. of Coomassie Acid Blue BL 150%. The half-hose were circulated at the boil for 30 minutes and the 54 gms. of sodium bichromate were added and the boiling continued for a further 30 minutes. A grey fleck effect was obtained.

(15) 6.35 kgrns. of white wool half-hose were scoured and then entered into a liquor having a pH of 3.7 and consisting of 158.6 litresof boiling water containing 245 ccs. of formic acid and 210 gms. of Erional NW, and circulated for 20 minutes. The half-hose were washed with water and entered intoa fresh liquor containing 158.6 litres of boiling water, 35 gms. of Erional NW, ccs. of 80% acetic acid, 182 gms. of Solochrome Yellow Y 125%, 84 gms. of Omega Chrome Bordeaux B (manufactured by Sandoz Products Ltd.) and 50 gms. of C00- rnassie Acid Blue RL and the half-hose circulated at the boil for 30 minutes. Then 130 gms. of sodium bichromate were added andthe boiling continued for a further 25 minutes. 70 gms. of Erio fast Red ZBLS and 20 gms. of Erie Anthracene fast Blue 4GL (both manufactured by The Geigy Colour Co., Ltd.) were dissolved in a little boiling Water and added, and the half-hose were boiled for a further 15 minutes. A brown ingrain effect was obtained.

(16) 680 gms. of white wool yarn were dyed by entering the yarn into a stainless steel Hussong Sample yarn dyeing machine containing a liquor having a pH of 3.8 and consisting of 149.5 litresof boiling Water having dissolved therein 2.95 gms. of Solochrome Red B 125%, 0.98 gm. of Solochrome Yellow Y 125% and 0.98 of Coornassie Acid Blue RL 150%, 125 ccs. of 80% acetic acid and 250 gms. of Erional NW. The liquor was circulated around the yarn and finally after 30 minutes 2 gms. of sodium bichromate was added and boiling continued for a further 30 minutes. A red-grey fleck effect was obtained.

(17) 1.81 kgms. of white wool yarn was entered into 149.5 litres of water in a yarn dyeing machine and scoured with 2% of Dispersol A- (an aqueous solution of a fatty alcohol ethylene oxide condensation product, manufactured by Imperial Chemical Industries, Ltd.) for 15 minutes with circulating liquor at 70 C. The yarn was then washed with water and raised from the bath. At bath was then prepared having a pH of 2.9 and containing 260 ccs. of 80% acetic acid, 65 gms. of Erional NW, 6.5 gms. of Solochrome Yellow L 125%, 6.5 gms. of S010- chrome Red B 125%, 14.56 gms. of Coomassie Acid Blue RL 150%, and 149.5 litres of water and brought to the boil. The yarn was re-entered into the bath and circulation of boiling liquor continued for a further 30 minutes. Then 6.5 gms. of sodium bichromate was added and boiling continued for a further 30 minutes with circulation. A grey tone-in-tone ingrain effect was obtained. Some of the yarn was knitted into fabric and a good ingrain effect was obtained.

(18) 3.06 kgms. of white wool yarn was secured as described in Example 17. Then a. bath was prepared having a pH of 3.2 and containing 153 ccs. of 80% acetic acid, 60 gms. of Erional NW, 2 grns. of Solochrome Red B 125 3 gms. of Solochrome Yellow Y 125 and 9 guns. of Coornassie Acid Blue RL 150% and 154 litres of water and brought to the boil. The yarn was entered into this bath and circulation of boiling liquor continued for a further 30 minutes. Then 2 gm. of sodium bichromate were added and boiling continued for a further 30 minutes with circulation. A good grey ingrain elfect was obtained.

(19) 240 gms. of white wool childrens socks were scoured and entered into an overhead paddle machine containing a liquor having a pH of 3.0 and consisting of 22.7 litres of boiling water having dissolved therein 40 gms. of Erional NW, 20 gms. of 80% acetic acid, 0.5 gm. of Solochrome Flavine G, and 0.5 gm. of Erie Anthracene Blue 4GL. After circulating for 30 minutes, 0.5 gm. of sodium bichromate was added and the boiling continued for a further 25 minutes. A two-colour greenblue/ yellowish melange efiect was obtained.

(20) 280 gms. of white wool half-hose were entered with circulation into a liquor having a pH of 3.2 and consisting of 22.7 litres of boiling water having dissolved therein 14 ccs. of 80% acetic acid, 4.2 gms. of Erional NW, 2.8 gms. of Neolan Blue 2R and 0.7 gm. of Ncolan Flavine GFE and dyeing continued at the boil for 1 hour. A striging two-colour contrast blue/ green melange effect was obtained similar to a Lovat half-hose which is normally obtained from two different dyeings of wool mixed in yarn at the spinners to give a two-colour effect.

(21) 280 gms. of white wool half-hose was entered into a liquor having a pH of 3.2 and consisting of 22.7 litres of boiling water containing dissolved therein 14 ccs. of 80% acetic acid, 14 ccs. of 25% Lissatan AC, 1 gm. of Solochrome Flavine G 150% and 1.5 gms. of Coomassie Acid Blue RL 150%. After boiling for 30 minutes 0.5 gm. of sodium bichromate was added and boiling continued fora further 30 minutes. A striking yellow-green/ blue-green melange effect was obtained.

(22) 280 gms. of white wool half-hose was entered into a liquor having a pH of 3.2 and consisting of 22.7 litres of boiling water containing dissolved therein 14 ccs. of 80% acetic acid, 4.2 gms. of Erional NW, 0.84 gm. of Naththalene Scarlet 4R8 (which contains three sulphonic acid groups), 0.84 gm. of Lissarnine Blue RS and 0.84 gm. of Metanil Yellow YKS (all manufactured by Imperial Chemical Industries, Ltd) After circulating and boiling for 60 minutes the half-hose were washed with water. A yellow-fawn and dark-brown two-colour melange eifect was obtained.

(23) 280 gms. of white wool half-hose was entered into a liquor having a pH of 3.2 and consisting of 22.7 litres of boiling water containing dissolved therein 14 ccs. of 80% acetic acid, 4.2 gms. of Erional NW, 0.28 gm. of Coornassie Acid Blue RL 150%, 0.56 gm. of A20 Rhodine 268 (Colour Index No. 31, manufactured by Sandoz Products, Ltd.) and 0.28 gm. of Metmiil Yellow YKS. After 60 minutes circulating the half-hose were washed in water. A three-colour effect was produced with two light fawns and a light purplish-brown melange effect.

(24) 7.47 kgms. of while wool half-hose was entered into a liquir having a pH of 3.4 and consisting of 158.6 litres of boiling water containing dissolved therein 273 ccs. of 80% acetic acid, 252 gms. of Erional NW, 48 gms. of Solochrome Flavine G 150%, 69 gms. of Coomassie Acid Blue RL 150% and 724 gms. of Alizarine Red AS powder (all manufactured by Imperial Chemical Industries, Itd.). After circulating at the boil for 30 minutes 111 gms. of sodium bichromate were added and dyeing continued at the boil for a further 30 minutes. A red heather mixture type rnelange effect was obtained in two colours, namely, bright red and blue-brown.

(25) 880 gms. of white halfihosemade from 'a mixture of 15% of Wool, 35% of Ardil and 50% of cotton were entered into a liquor having a pH of 3.3 and consisting of 22.7 litres of boiling water having dissolved therein 40 ccs. of acetic acid, 20 gms. of Erional NW, 0.29 gm. of Solochrorne Red B 0.64 gm. of Solochrome Yellow Y 125%, and 1.4 gins. of Coomassie Acid Blue RL After circulating for 30 minutes an addition of 0.46 gm. of sodium bichromate was made and the boiling continued for a further 30 minutes. A greyish fleck effect was obtained on the wool and ardil, whilst the cotton Was practically unstained.

(26) A mans white pullover made of wool and cotton and weighing 196 grams. was entered into an overhead paddle machine containing a liquor having a pH of 3.2 and consisting of 22.7 litres of water having dissolved therein 10 ccs. of 80% acetic acid, 2 gms. of Eiional NW, 1.5 gms. of Neolan Yellow BE, 6 guts. of Neolan Blue 2R, 2 grns. of Neolan Flavine GFE (all manufactured by the Clayton Aniline Co., Ltd), and 1 gm. of Pyrochrome Red B (sold by Messrs. Bernard Keegan, Ltd). After circulating at the boil for 60 minutes the pullover was washed in cold water. A two-colour melange effect was obtained and the cotton was unstained.

(27) 805 kgms. of girls white three-quarter-hose made of wool plated on cotton were entered into a Gorrie machine containing a liquor having a pH of 3.2 and consisting of 1827 litres of water at the boil having dissolved therein 4.02 kgms. of 80% acetic acid, 841 gms. of Erional NW, 244 gms. of Solochrome Yellow Y 125%, gms. of Solochrorne Red B 125% and 101 grns. of Coomassie Acid Blue RL 150%. The threequarter hose were boiled for 30 minutes and then 200 gms. of sodium bichromate were added and the boiling continued for a further 30 minutes. The three-quarter hose were then washed in water, hydro-extracted, and re-entered into the dyeing machine containing water, 730 gms. of Thiotan RS (manufactured by Sandoz Products, Ltd.), 250 gms. of Solar Grey WFK (manufactured by Sandoz Products, Ltd.) and 525 gms. of Diphenyl Fast Brown DFI-I (manufactured by The Geigy Colour Co., Ltd.) at a temperature of 60 to 171 C. and the dyeing was continued for a further 40 minutes. A fleck eifect Was produced in the wool and the cotton was dyed in tone.

(28) 12 gms. of white wool 6/3 rib half-hose were entered into a liquor having a pH of 3.1 and consisting of 300 ccs. of boiling water containing dissolved therein 17 ccs. of 8% acetic acid, 17 ccs. of a 2% Erional NW solution, 5 ccs. of a 2% Carrnoisine LS solution, and 3.5 ccs. of a 2% sodium bichromate solution. After boiling for one hour the half-hose were washed in water. A bluish-lilac fleck effect was obtained.

(29) 12 grns. of White wool half-host were entered into a liquor having a pH of 3.1 and consisting of 300 ccs. of boiling water having dissolved therein 17 ccs. of a 2% solution of 2-naphthol-3.6-disulphonic acid, 17 ccs. of 8% acetic acid, 10 ccs. of 213.75% solution of formaldehyde, and 5 ccs. of a 2% solution of Carrnoisine LS. After boiling for one hour a blue-violet fleck effect was obtained.

(30) 12 gins. of white wool half-hose were entered into a liquor having a pH of 3.1 and consisting of 300 ccs. of boiling water containing dissolved therein 0.2 gm. of Neolan Blue 26 which has the formula and 0.3 gm. of Neolan Yellow GR, 13 of 8% acetic acid and 13.5 ccs. of a 2% solution of Erional NW. After boiling for one hour the half-hose were washed in cold water. A grass green and dark green tWo-colour melange effect was obtained.

(31) 12 gms. of white wool half-hose were entered into a liquor having a pH of 3.2 and consisting of 300 ccs. of boiling water having dissolved therein 0.7 gm. of paraformaldehyde, 6.2 ccs. of8% acetic acid, 6.2 ccs. of a 10% solution of Erional NW and 0.25 gm. of Carmoisine LS. After boiling for 30 minutes, 6 ccs. of a 2% sodium bichromate solution was added and boiling continued for a further 30 minutes. A melange effect in dark blue was obtained.

(32) 22 gms. of white wool half-hose were entered into a liquor having a pH of 3.7 and consisting of 500 ccs. of boiling water having dissolved therein 66 ccs. of 10% formic acid and 44 ccs. of a 2% solution of Erional NW. The pH of the bath was 3.8 and boiling was effected for 20 minutes. The half-hose were then washed in cold water and re-entered into 660 cos. of boiling water containing 4.4 ccs. of 8% acetic acid and 0.44 gm. of Eriochrome Green HK and boiled for 30 minutes. Then 11 ccs. of a 2% sodium bichromate solution was added and the boiling continued for a further 30 minutes. A green fleck effect was obtained.

(33) 22 gms. of white wool half-hose were entered into a liquor having a pH of 3.4 and consisting of 500 ccs. of boiling water containing dissolved therein 8.8 ccs. of 8% acetic acid and 44 ccs. of a 2% solution of Erional NW. The pH of the bath was 4.2. The liquor was heated at the boil for 20 minutes. The half-hose were then washed in cold water and re-entered into 660 ccs. of boiling water having dissolved therein 4.4 ccs. of 8% acetic acid and 0.44 gm. of Eriochrome Green HK, and boiled for 30 minutes. Then 11 ccs. of a 2% sodium bichromate solution was added and boiling continued for a further 30 minutes. A green fleck effect was obtained.

(34) 22 gms. of white wool half-hose were entered into 500 ccs. of boiling water having dissolved therein 4.4 ccs. of 9.6% sulphuric acid and 44 ccs. of a 2% solution of Erional NW, the solution having a pH of 2.5. The liquor was heated at the boil for 20 minutes, and the half-hose were then washed in cold water.

The half-hose were then re-entered into a liquor having a pH of 2.8 and consisting of 660 ccs. of boiling water containing 4.4 ccs. of 8% acetic acid and 0.44 gm. of Eriochrome Green HK and boiled for 30 minutes. Then 11 ccs. of a 2% solution of sodium bichrornate were added and the boiling continued for a further 30 minutes. A green fleck effect was obtained.

(35) 22 gms. of white wool half-hose were entered into a liquor having a pH of 2.8 and consisting of 500 ccs. of boiling water having dissolved therein 6.6 ccs. of formic acid, 0.44 of formaldehyde and 44 ccs. of a 2% Erional NW solution. The [pH of the solution was 3.8 and it was heated to the boil for 20 minutes. The half-hose were then Washed in cold water and then dyed as in Example 58. A green fleck effect was obtained.

(36) 22 gms. of white wool half-hose were entered into a liquor having a pH of 2.8 and consisting of 500 ccs. of boiling water having dissolved therein 6.6 ccs. of formic acid, 0.88 gms. of 2-naphthol-3.6-disodium sulphonate and 44 ccs. of a 2% solution of Erional NW. The pH of the solution was 3.8. The half-hose were heated for 20 minutes at the boil and were then washed in cold water, and dyed as in Example 34. A green effect was obtained.

(37) 22 gms. of white wool half-hose were entered into a liquor having a pH of 2.8 and consisting of 500 ccs. of boiling water having dissolved therein 6.6 ccs. of formic acid and 0.88 gm. of Azoguard solution (a 35% aqueous solution of a sodium salt of a naphthalene trisulphonic acid) and 44 ccs. of a 2% solution of Erional NW. The whole was boiled for 20 minutes. The halfa light fawn melange effect.

hose were then washed'w'ith cold water and dyed as in Example 34. A green fleck effect was obtained.

(38) 22 gms. of white wool half-hose were entered into a liquor having a pH of 2.8 and consisting of 500 ccs. of boiling water having dissolved therein 6.6 ccs. of 8% formic acid, 0.44 gm. of formaldehyde, 0.44 gm. of Azoguard solution (a 35% aqueous solution of a sodium salt of a naphthalene trisulphonic acid) and 22 ccs. of a 2% solution of Erional NW, and the whole was heated for 20-minutes at the boil. The half-hose were then washed in cold water and dyed as in Example 34. A green fleck effect was obtained.

(39) 33.5 kgms. of childrens'white wool socks were scoured with soap, washed and entered into a liquor having a pH of 3.3 and consisting of 761 litres of boiling water having dissolved therein 730 gms. of a detergent, Falco ELA (manufactured by the Arno Chemical Co. Ltd.), 1.46 kgm. of 80% acetic acid, 730 gms. of Lissatan F, 21.8 gms. of Solochrome Yellow Y 21.8 gms. of Solochrorne Red B 125 and 6.5 gms. of Coomassie Acid Blue RL After boiling for 30 minutes, 22 gms. of sodium bichromate were added and a further 30 minutes boiling continued. The socks then showed "In this case a slightly darker fawn was required, and as by this method it is easily possible to top up or add fast type acid dyestuffs, or Coomassie type dyestuffs of a certain type (i.e. containing two or more sulphonic groups) without spoiling the effect, 8 gms. of Eric Fast Yellow GLS, 8 gms. of Erio Anthracene Blue 4GL and 2 gms. of Eric Fast Red ZBLS 125% were added, and boiling continued for a further 15 minutes. A very good fawn fleck effect was obtained.

(40) 48.7 kgms. of white wool half-hose with nylon splicing at the heel and toe and with fancy cotton clocking on the leg were entered into a liquor having a pH of 3.2 and consisting of 1382 litres of boiling water having dissolved therein 31.5 gms. of Cibacet Yellow GBA Extra (manufactured by Imperial Chemicals Ltd.), 819 gms. of Erio Fast Yellow GLS (manufactured by The Geigy Colour Co. Ltd.), 630 gms. of Omega Chrome Bordeaux B, 378 gms. of Coomassie Acid Blue RL 150%, 2,636 litres of 80% acetic acid, 1,386 kgms. of Lissatan F and 25.2 gms. of Erional NW, and the dyeing continued at the boil for 30 minutes with the addition of 1,088 litres of Falco ELA New, which is a detergent scour and wetting agent. After 30 minutes, 315 gms. of sodium bichromate were carefully added and dyeing continued for a further 30 minutes. As the nylon did not match 5 gms. of Cibacet Scarlet BS and 8 gms. of Cibacet Yellow GBA Extra (both manufactured 'by Imperial Chemical Industries, Ltd.) were added and dyeing continued for a further 20 to 25 minutes, when a match on the nylon splicing was obtained. A very good effect was produced. Afterwards the half-hose were treated by an alkaline chlorination shrink-resist process without visible alteration of colour or of the melange effect obtained.

(41) 68.4 kgms. of white wool half-hose with nylon splicing in the toe and heel were scoured in a Tom Tom beater with 1.36 kgms. of Garbritol SE (a detergent manufactured by The Gardinol Chemical Co. Ltd., which is a sodium salt of a mixture of sulphonated fatty alcohols) at 71 C. for 15 minutes with the heaters working. The half-hose were then rinsed and hydro-extracted.

The half-hose were then entered into an overhead paddle dyeing machine made of stainless steel and containing a liquor having a pH of 3.2 and consisting of 1450 litres of boiling water having dissolved therein 3.4 kgs. of 80% acetic acid and 1.7 kgms. of Erional NW, 580 gms. of Eriochrome Green HK and 9 gms. of C00- massie Acid Blue RL 150%. After dyeing at the boil for 30 minutes, 288 gms. of sodium bichromate were added and boiling continued for a further 30minutes. A good green ingrain fleck effect was obtained with the nylon splicing in the toe and heel undyed. v,

(42) Heavy white wool half-hose (weighing over 1.5 kgms. per dozen pairs) made on 84 needle circular knitting machines were treated as follows: 800 gods. of the heavy white wool half-hose were entered into 22.7 litres of boiling water having dissolved therein 24 gms. of formaldehyde and 24 cos. of 80% acetic acid, and boiled for minutes. After rinsing, the half-hose were treated in a warm bath containing 8 gms. of sodium bisulphite. The half-hose were then entered into a liquor having a pH of 3.7 and consisting of 22.7 litres of boiling water having dissolved therein ccs. of 80% acetic acid and 8 ccs. of Lissatan F, 11.25 gms. of Carmoisine LS, 6.8 gms. of Coomassie Acid Blue R-L 150% and 4 gms. of Alizarine light blue 4 'GL (Colour Index No. 1054, made by Sandoz Products, Ltd.) and boiling continued for a further 30 minutes. Then 5.5 gms. of sodium bichromate were added and the boiling continued for a further 30 minutes. 7 A navy blue fleck effect was obtained.

(43) "400 gms. of white wool half-hose were pre-boiled in 4% of concentrated formic acid, 2% of Lissatan F and 0.5% of Erional NW, all calculated on the weight of the half-hose, in 22.7 litres of boiling water for 20 minutes. The half-hose were washed withwater and rinsed and hydro-extracted. They were then entered into 22.7 litres'of water at 71 C., the water having dissolved therein 1% of 80% formic acid and 2% of sodium bichromate, calculated on the weight of the half-hose, and raised slowly to the boil. The boiling was continued for minutes and the half-hose were then washed with cold water. The half-hose were re-entered after hydro-extraction, into a liquor having a pH of 3.2 and consisting of 22.7 litres of boiling water having dissolved therein 2% of 80% acetic acid and 1% of Lissatan F, calculated on the weight of the half-hose, and 4 gms. of Alizarine Brilliant Blue B (Colour Index No. 1054, manufactured by The Yorkshire Dyeware and Chemical Co. Ltd.). A very good green-blue effect was obtained which on back scouring with soap at 54 to C. gave a good result.

(44) 400 gms. of white wool half-hose were entered at the boil into a paddle dyeing machine containing a liquor having a pH of 3.2 and consisting of 22.7 litres of water having dissolved therein 20 gms. of 80% acetic acid, 6 gms. of Lissatan F, 4 gms. of triethanolamine, 0.4 gm. of Solochrome Red B 125 0.96 gm. of Solochrome Yellow 1 125% and 1.12 gm. of Coomassie Acid Blue RL 150%, and the boiling continued for 30 minutes. an 0.66 gm. of sodium bichromate was added and the half-hose boiled for a further 30 minutes. The half-hose were then rinsed with cold water and a grey fleck efiect was obtained.

(45) 400 gms. of white wool knitted fabric was entered into a liquor having a pH of 3.7. and consisting of 22.7 litres of boiling water having dissolved therein 20 ccs. of 80% acetic acid, 8 ccs. of Lissatan F and 16 gms. of Neolan Blue 2R, and the dyeing was continued boil for SO'minutes. A blue fleck efliect was obtained.

(46) 200 gms. of yarn consisting of a mixture of wool and Ardil were entered into a liquor having a pH of 3.7 and consisting of 22.7 litres of boiling water having dissolved therein 4 cos. of Lissatan F and 10 cos. of 80% acetic acid, together with 8 gms. of Neolan Blue 2R. Dyeing was continued at the boil for 60 minutes. Both the wool and the Ardil were dyed with a fleck effect.

(47) 200 gms. of white 'wool gloves, after scouring with soap and ammonia and rinsing and hydro-extracting, were entered into a paddle dyeing machinecontaining a liquor having a pH of 3.2 and consisting of 22.7 litres of water having dissolved therein 10 ccs. of 80% acetic acid, 4 ccs. of Lissatan F and 8 gms. of Neolan Blue 2R. The dyeing was continued for 60 minutes at the boil. The gloves were dyed blue with a fleck effect.

(48) 400 gms. of heavy 84 needle machine-made white wool half hose were entered into a liquor having a pH of 3.2 and consisting of 22.7 litres of water at a temperature of 60 C. and 20 ccs. of 80% acetic acid,'10

at the 112 ccs. of Lissatan F, 0.24 gm. of Solochro'me Red B 125 0.5 gm. of Solochrome Yellow Y 125% and 0.9 gm. of Coomassie Acid Blue RI. 150%. After boiling for 30 minutes, 4.5 gms. of sodium bichromate were added and circulation of the liquor was maintained for a further 30 minutes. A grey fleck efiect was obtained.

(49) 400 gms. of heavy white wool half-hose were entered into a liquor having a pH of 3.2 and consisting of 22.7 litres of water at a temperature of 49 C. and 20 ccs. of acetic acid, 10 ccs. of Lissatan F and 1.0 gm. of Coornassie Acid Blue RL 150%, and circulation of the half-hose in the liquor was maintained for 50 minutes. A blue fleck effect was obtained.

(50) gms. of white wool half-hose were entered into a liquor having a pH of 3.4 and consisting of 3 litres of boiling Water having dissolved therein 0.85 gm. of Solochrorne Cyanine R 200%, 0.85 gm. of Solochrome Yellow G 150% and 0.45 gm. of Solochrome Red ERS (Colour Index No. 652) (all dyestufli's manufactured by imperial Chemical Industries, Ltd), with 3.5 ccs. of 80% acetic acid and 3.3 gms. of Erional NW, and boiling and circulation continued for 30 minutes. Then 2 gms. of potassium bichromate were added and boiling continued for a further 30 minutes. A very good twocolour melange efiect was obtained.

(51) 8 gms. of white wool half-hose were dyed at the boil with a liquor having a pH of 3.2 and consisting of 300 ccs. of boiling water having dissolved therein 0.33 gm. of Lissatan AC, 0.41 gm. of 80% acetic acid, 0.033 gm. of Chromosol Green EB (manufactured by Sandoz Products, Ltd), 0.033 gm. of Solochrome Red B and 0.33 gm. of Alizarine Pure Blue B (Colour Index No. 1088) (made by L. B. Holliday & Co. Ltd.). After 30 minutes, 0.1 gm. of sodium bichromate was added and the boiling continued for a further 30 minutes. A two colour melange eifect was obtained.

(52) 8 gms. of white wool half-hose were entered into a liquor having a pH of 3.2 andconsisting of 300 ccs. of boiling water with 4 cos. of 8% acetic acid, 6.5 ccs. of Lissatan F, 0.06 gm. of Solochrome Yellow G 0.06 gm. of Solochrome Blue PE 150% and 0.06 gm. of Solochrorne Red B 125 After boiling for 30 minutes, 0.1 gm. of sodium bichromate was added and the boiling continued for a further 30 minutes. A two-colour yellow and red-blue melange effect was obtained.

(53) '400 gms. of white wool half-hose were entered into a bath having a pH of 3.2 and containing 22.7 litres of boiling water having dissolved therein 0.4 gm. of Solochrome Red B 125%, 0.96 gm. of Solochrome Yellow Y 125%, 1.12 gms. of Coomassie Acid Blue RL 150%, 20 cos. of 80% acetic acid and 8 gms. of Paramel A (a syntan containing a water-soluble melamineformaldehyde condensation product). Boiling was continued for 30 minutes and then 0.65 gm. of sodium bi chromate was added and boiling continued for a further 30 minutes. A good grey fleck effect was obtained.

(54) Example 53 was repeated but the 8 gms. of 'Paramel A was reduced to 4 gms. and 6 gms. of Lissatan F was also added. A good grey fleck effect was obtained.

(55) 350 gms. of white wool half-hose and 50 gms. of white knitted wool fabric were entered into a liquor having a pH of 3.3 and consisting of 22.7 litres of boiling water containing 16 ccs. of 80% acetic acid, 8 ccs. of Lissatan F, 2 ccs. of Erional NW, 0.2 gm. of S010- chrome Flavine G, 0.4 gm. of Solochrome Red B 125% and 0.3 gm. of Coomassie Acid Blue RL 150%, and boiled for 30 minutes. Then 0.25 gm. of sodium bichromate was added and boiling continued for a further 30 minutes. A two-colour light-fawn/lilac-brown melange effect was obtained.

(56) 12 gms. 0f white wool half-hose were entered into a liquor having a pH of 3.1 and consisting of '300 ccs. of boiling water having dissolved therein 13.5 ccs. of a 2% Erional NW solution, 13 ccs. of 8% acetic acid and 3 ccs. of a 2% =Neolan Black 2R solution, and dye- 13 ing was continued at the boil for white fleck effect was obtained.

(57) 400 gms. of white Wool half-hose were boiled for 50 minutes in a liquor having a pH of 3.7 and consisting of 22.7 litres of water having dissolved therein 0.5% of Glyoxal (50% w./w.), 1.5% of Lissatan F, 3% of 80% acetic acid and 1% of Coomassie Acid Blue 150% (all calculated on the weight of the half-hose). A good blue fleck effect was obtained.

(58) 400 gms. of white wool half-hose were entered into a liquor having a pH of 3.7 and consisting of 22.7 litres of boiling water having dissolved therein 0.4 gm. of Solochrome Red B 125%, 0.96 gm. of Solochrome Yellow Y 125%, 1.12 gms. of Coomassie Acid Blue RL 150%, 12 gms. of 80% acetic acid and 4 gms. of Paramel A. Boiling was continued for 30 minutes and then 0.65 gm. of sodium bichromate was added and boiling continued for a further 30 minutes. A grey fleck effect was obtained.

(59) 400 gms. of white wool half-hose were pre-boiled for 20 minutes with 4% of 85% formic acid and 2% of Erional NW, both calculated on the weight of the half-hose, and entered into 22.7 litres of water the liquor having a pH of 2.8. After washing and neutralising with 2% of a 0.66% solution of sodium sesquicarbonate, calculated on the weight of the half-hose, the half-hose were hydro-extracted and entered at the boil into a fresh bath containing 12 gms. of Lissatan F and 4 gms. of Coomassie Green T 150% and boiled for 45 minutes. A blue-green fleck effect was obtained.

(60) 400 gms. of white wool half-hose made of a mixture of wool and rayon were entered into a liquor having a pH of 3.2 and consisting of 22.7 litres of boiling water having dissolved therein 20 ccs. of 80% acetic acid, 8 gms. of Lissatan F, 4 gms. of Erional NW, 4 gms. of Neolan Blue 2R and 1 gm. of Neolan Flavine GFE, and the boiling was continued for 30 minutes. The rayon was white and a two-colour melange eifect of dark blue-green and lighter green was obtained on the wool.

(61) 200 gms. of white wool gloves were dyed at the boil with a liquor having a pH of 3.1 and consisting of 20 ccs. of 80% acetic acid, 6 gms. of Erional NW, 4 gms. of Neolan Blue 2R and 1 gm. of Neolan Flavine GFE in 22.7 litres of water. Boiling was continued for 50 minutes. A two-colour blue-green and yellower green eflect was obtained. Also present in the dyebath was a small quantity of yarn of wool and Ardil, wool fabric and wool yarn. All showed the same two-colour melange effect.

(62) 33 kgms. of white wool half-hose were entered at the boil with 1.15 litres of Falco ELA, 453 gms. of Erional NW and 1.36 kgms. of 80% acetic acid and 453 gms. of 80% formic acid into a paddle dyeing machine containing 760 litres of boiling water, 192 gms. of Neolan Blue 2R, 48 gms. of Neolan Red BRE, 97 gms. of Neolan Yellow 8GB and 97 gms. of Neolan Flavine GFE the liquor having a pH of 3.4. After 20 minutes, 575 ccs. of 85% formic acid were added and then after 30 minutes 150 gms. of Neolan Blue 2R, 90 gms. of Neolan Red BRE and 60 gms. of Neolan Yellow 8GB were added carefully after dissolving in boiling water. After 60 minutes further boiling a good brown threecolour melange effect was obtained.

(63) 453 gms. of white wool yarn was entered into a Staybrite Hussong Dyeing Machine containing a liquor having a pH of 3.2 and consisting of 155 litres of water at 71 C. having dissolved therein 57 gms. of Falco ELA, 22 ccs. of 80% acetic acid, 9 ccs. of Lissatan F, and 40 gms. of Neolan Blue 2R and 20 gms. of Neolan Flavine GFE, and the liquor was brought to the boil in minutes. After boiling for 45 minutes the yarn was raised and rinsed in cold water. A yellow-green and blue-green melange effect was obtained.

(64) 400 gms. of a mixture of white wool half-hose 50 minutes. A greyishand a'small-piece of white wool fabric were entered into an overhead paddle machine containing a liquor having a pH of 3.2 and consisting of 22.7-litres of boiling water having dissolved therein 20 ccs. of acetic acid, 1 cc. of Lissatan F, 0.4 gm. of Solochrome Red B 125%, 0.96 gm; of Solochrome Yellow Y 125% and 1.12 gm. of Coomassie Acid Blue RL 150%. The boiling was continued for 30 minutes and then 0.65 gm. of sodium bichromate was added and the boiling continued for a further 30 minutes. A grey melange efiect was obtained.

(65) Example 64 was repeated but using only 12 ccs. of 20% acetic acid and 0.4 cc. of Lissatan F. A slight grey melange elfect was obtained.

(66) A piece of white wool half-hose was printed as follows: A paste containing parts by weight of aluminium sulphate, 100 parts by weight of water and 300 parts by weight of an 8% solution of gum tragacanth was made up. 5 gms. of this was used and 0.2 ccs. of 80% acetic acid was mixed therewith the paste having a pH of 3.4. The half-hose was then printed in a pattern with this paste, dried and steamed for 5 minutes, and finally washed in cold water.

The half-hose was then dyed at the boil with 2% of Erional NW, 1% of Erio Anthracene Blue 4GL (both percentages being calculated on the weight of the halfhose) for 30 minutes. The half-hose was dyed dark blue on the pattern part with a fleck effect and the remainder of the half-hose was dyed light solid blue. After washing with cold water, the half-hose was dried.

(67) A piece of white wool fabric was printed with a pattern using a paste of the following composition; 6 gms. of aluminum sulphate, 6 gms. of water, 18 gms. of an 8% gum tragacanth, 0.2 ccs. of 80% acetic acid, 0.3 gm. or Erional NW and 0.1 gm. of Coomassie Acid Blue RL 150% the paste having ,a pH of 3.4. The fabric was then dried, steamed for 5 minutes and washed in cold water. A blue fleck pattern on a white ground was obtained.

('68) 400 gms. of wool fabric were dyed at the boil with a liquor having a pH of 3.4 and consisting of 16 gms. of 80% acetic acid, 8 gms. of Erional NW and 4 gms. of Carmoisine LS, in 22.7 litres of water, for 40 minutes. The fabric was then washed and dried.

Apiece of the dried wool fabric was then printed with a Formosol discharge paste made up of 4.5 gms. of Formosol, 0.6 gm. of glycerine, 6 gms. of water and 18 gms. of a 7% gum tragacanth solution. The fabric was then dried, steamed for 5 minutes, washed in cold Water'and redried. A white printed pattern on a claret red fleck effect ground was obtained.

(69') 400 gms. of white wool half-hose were entered into 22.7 litres of boiling Water having dissolved therein 16 gms. of lactic acid, 8 gms. of Lissatan F and 4 gms. of Coomassie Acid Blue RL 150%. After boiling for 50 minutes ablue fleck effect was obtained.

(70) 400 gms. of white wool half-hose were boiled with 8 gms. of benzoquinone for 1 hour in 22.7 litres of water. After washing the half-hose were dyed with 16 gms. of 80% acetic acid, 8 gms. of Lissatan F and 4 gms. of Coomassie Acid Blue RL 150% in 22.7 litres of water the liquor having a pH of 3.4. A brown/blue eifect was obtained.

(71) 400 gms. of white wool half-hose were entered into a liquor having a pH of 3.4 and consisting of 22.7 litres of water at 71 C. with 16 gms. of acetic acid, 8 gms. of Lissatan F, 2 gms. of Erional NW, 0.8 gm. of Solochrome AzurineB 150% and 1.6 gm. of Solochrome Red B After heating for 30 minutes 1.2 gm. of sodium bichromate was added and the heating at 71 C. continued for a further 30 minutes. A lilac and red two-colour melange eifect was obtained.

(72) 400 gms. of white wool half-hose was entered into a vat containing a liquor having a pH of 3.4 and consisting of 22.7 litres of water having dissolved therein 1.6 gms. of Solochrome RedB 125%, 3.84l gnls. of Solochrome Yellow Y 125%, 4.48 guns of Coomassie. Acid Blue RL 150%, 16 ccs. of 80% acetic acidand 6-. gins. of Basyntan Extra K (a condensation product of polyhydric phenols and an aromatic sulphonic acid, sold by Messrs. Bush, Beach and Gent, Ltd.). The boiling was continued for 30 minutes and then 2.8 gins. of sodium bichromate were added and the, boiling. continued for a further 30 minutes. A grey fleck efiect was obtained.

(73) 400 gms. of white wool fabric was dyed in a liquor having a pH of 3.5 and consisting of 22.7 litres of boiling water having dissolved therein 14 ccs. of. 80%. acetic acid, 6 gms. of sulphanilic acid, 8 cos. of formaldehyde and 4 guns. of Eric Fast Red 2 BLS 125%, for 40 minutes. A good red ingrain eifect was obtained.

(74) 8 gins. of white wool half-hose was entered into a liquor having a pH of 3.5 and consisting of 300 ccs. of boiling water having dissolved therein 0.01 gm. of Solochrome Red B 125%, 0.03 gm. of Coornassie Acid Blue RL 150%, 0.02 gm. of Solochrome Yellow Y 125%, 0.1

gm. of benzidine, 0.5 cc. of formaldehyde and 0.4 cc. of 96% sulphuric acid. Boiling was continued for 25 minutes and then 0.03 gm. of sodium bichromate was added and the dyeing continued for a further 25 minutes. A fawn ingrain effect was obtained.

(75) 8 gins. of white wool half-hose was boiled for 10 minutes in 300 ccs. of boiling water containing 0.5 cc. of formaldehyde. The pH of the solution was adiusted to 8 by the addition of ammonia. The wool was removed, washed with water until neutral and then boiled for 25 minutes in a liquor having a pH of 3.4 and consisting of 300 cos. of water containing dissolved therein 0.01 gm. of Soloc hrome Red B 125%, 0.03 gm. of Solochrome Yellow Y 125%, ccs. of a aqueous solution of Lissatan F and 3.3 cos. of 8% acetic acid. Then 0.3 gm. of sodium bichrornate was added and the boiling continued for a further minutes. A grey in-, grain eifect was obtained.

(76) Example 75 was repeated but in the treatment with formaldehyde the pH was adjusted. to 9.2. A grey ingrain effect was obtained.

The process of the present invention has a number of advantages. Thus, it enables an effect similar to the ingrain effect to be produced starting from white unchlorinated wool yarn which can be dyed toany desired shade.

The dyed wool of the present invention is softer,

' has a better handle, better wearing qualities and lower heat conductivity than the same wool before dyeing or the same wool dyed by conventional processes particularly by the so-called Vibriol dyeing involving dyeing in the presence of sulphuric acid.

Furthermore, as indicated above, two or more colour effects can be produced in addition to the ingrain effect, thus producing, for example, the well-known Heather Mixture effect.

It wool goods or fabrics are treated by the present inventionusing a printing process, various patterns or designs are possible in fleck or two or more colour eifects.

in the appended claims the term dyeing includes printing and the term solution includes paste.

This application is a continuation-in-part of my appiication Serial No. 238,377, filed July 24, 1951, now abandoned.

What I claim is:

1. A process for non-uniformly dyeing a wool textile material whose wool content consists: substantially entirely of normal wool fibres which comprisestreating said textile material, in the absence of chlorinated wool and other forms of wool treated to alter the dyestufi affinity thereof as compared to normal wool, with an aqueous solution containing a condensation product which renders some of the amino acids present in Wool at least partially resistant to dyeing with dyestufis which normally dye wool, said condensation product being selected from they I group consisting of condensationproducts of aldehydes and aromatic sulphonic acids. and water-soluble salts of condensation products of aldehydes and aromatic sulphonic acids, a water-soluble organic aliphatic acid which is non-injurious-to wool and at least one dyestuft which will dye wool and which contains at least two sulphonic acid groups in the molecule, the said aqueous solution having an initial pH of between 2.8 and 4.9.

2. A process as claimed in claim 1 wherein the watersoluble organic aliphatic acid is acetic acid.

3. A process as claimed in claim 1 wherein the watersoluble organic aliphatic acid is formic acid.

4'. A process as claimed in claim 1 wherein the aromatic sulphonic acid is a benzene sulphonic acid and the aldehyde is formaldehyde.

5. A process as claimed in claim 1 wherein the aromatic sulphonic acid is a naphthalene sulphonic acid and. the aldehyde is formaldehyde.

6. A process as claimed in claim 1 wherein the aromatic sulphonic acid is a phenol sulphonic acid andthe aldehyde is formaldehyde.

7. A process as claimed in claim 1 wherein the aromatic sulphonic acid is a naphthol sulphonic acid and the aldehyde isformaldehyde.

8. A process for non-uniformly dyeing a wool textile material whose wool content consists substantially entireiy of normal wood fibres which comprises treating said textile material, in the absence of chlorinated wool and other forms of, wool treated to alter the dyestufi affinity thereof as compared to normal wool, with an aqueous solution containing a condensation product which rendens some of the amino acids present in wool at least partially resistant to dyeing with dyestufis which normally dye wool, said condensation product being selected from the group consisting of condensation products of aldehydes and aromatic sulphonic acids and water-soluble salts of condensation products of aldehydes and aromatic sulphonic acids and a water-soluble organic aliphatic acid which is non-injurious to wool, and thereafter dyeing the thus treated wool with at least one dyestuii which will dye wool and which contains at least two sulphonic acid groupsin the molecule, the said aqueous solution having an initial pH 'of between 2.8 and 4.9.

9.' A process for non-uniformly dyeing a wool textile material whose woolcontent consists substantially entirely ofnormal' wool fibres which comprises treating said textile material, in the absence of chlorinated wool and other forms of wool treated to alter the dyestufi afiinity thereof-as compared to normal wool, with an aqueous solution containing a condensation product which renders some or" the amino acids present in wool at least partially resistant to dyeing with dyestuffs which normally dye wool, saidcondensation product being selected from the group consisting of condensation products of aldehydes and aromatic sulphonic acids and water-soluble salts of condensation products of aldehydes and aromatic sulphonic acids, and then treating the wool with an aqueous solution containing a water-soluble organic aliphatic acid which is nondnjurious to wool and at least one dyestufi which will dye wool and which contains at least two sulphonic acid groups in the molecule, the said aqueous solution containing said acid having an initial pH of between 2.8- and-4.9.

10. A process for non-uniformly dyeing-a wool textile material whose wool content consists substantially entirely of normal wool fibres which comprises treating said textile material, in the absence of chlorinated wool and other forms of wool treated to alter the dyestufli afiinity thereof as compared to normal wool, with an aqueous solution containing a water-soluble organic aliphatic acid which is non-injurious towool, the said aqueous solution having an initial pH of between 2.8 and 4.9, then treating the wool with an aqueous solution containing a condensa tion product which renders some of the amino acids present in the wool at, least partially resistant to dyeing with dyestufis which, normally dye wool, said condensation :17 product being selected from the group consisting of condensation products of aldehydes and aromatic sulphonic acids and water-soluble salts of condensation products of aldehydes and aromatic sulphonic acids, and then treating the wool with at least one dyestufl which will dye wool and which contains at least two sulphonic acid groups in the molecule.

11. A process for non-uniformly dyeing a wool textile material whosewool content consists substantially entirely of normal fibers which comprises treating said textile material, in the absence of chlorinated wool and other forms of wool treated to alter the dyestufr aflinity thereof as compared to normal wool, with an aqueous solution of sulphuric acid, washing the textile material and then treating the washed textile material with an aqueous solution containing a condensation product which renders some of the amino acids present in wool at least partially resistant to dyeing with dyestuffs which normally dye wool, said condensation product being selected from the group consisting of condensation products of aldehydes and aromatic sulphonic acids and water-soluble salts of condensation products of aldehydes and aromatic sulphuric acids, a water-soluble organic aliphatic acid which is non-injurious to wool and at least one dyestufi which will dye wool and which contains at least two sulphonic acid groups in the molecule, the said aqueous solution having an initial pH of between 2.8 and 4.9.

12. A process for non-uniformly dyeing a wool textile material whose wool content consists substantially entirely of normal wool fibers which comprises treating said textile material, in the absence of chlorinated wool and other forms of wool treated to alter the dyestufi" afiinity thereof as compared to normal wool, with an aqueous solution containing a condensation product which renders some of the amino acids present in wool at least partially resistant to dyeing with dyestuffs which normally dye wool, said condensation product being selected from the group consisting of condensation products of aldehydes and aromatic sulphonic acids and water-soluble salts of condensation products of aldehydes and aromatic sulphuric acids, a water-soluble organic aliphatic acid which is non-injurious to wool and at least one dyestuff which will dye wool and which contains at least two sulphonic acid groups in the molecule, the said aqueous solution having an initial pH of between 3.4 and 4.5.

13. A process as claimed in claim 1 wherein the dye bath additionally contains a dyestufi containing less than two sulfonic acid groups in the molecule.

14. A process as claimed in claim 1 wherein the dye bath is free from Glaubers salt and the initial pH is between 3.4 and 4.5.

15. A process as claimed in claim 1 wherein the dye bath additionally contains a dyestuff containing less than two sulfonic acid groups in the molecule and is free from Glaubers salt.

vl6. A process for non-uniformly dyeing a textile mate rial selected from the group consisting of yarns and fabrics made from such yarns, said textile material being composed substantially entirely of normal wool fibers, which comprises treating said textile material in the'absence of chlorinated wool and other forms of wool treated to alter the dyestuff afiinity thereof, as compared with said normal wool with an aqueous solution containing from about 1% to about 5%, calculated on the weight of the wool, of a condensation product which renders some of the amino acids present in wool at least partially resistant to dyeing with dyestuffs which normally dye wool, said condensation product being selected from the group consisting of condensation products of formaldehyde and aromatic sulphonic acids, and water-soluble salts of condensation products of formaldehyde and aromatic'sulphonic acids,- from about 2% to about 10%, calculated as acid and calculated on the weight of the wool, of a water-soluble organic aliphatic acid which is non-injurious to wool; and at least one dyestuif which will dye wool and which contains at least two sulphonic acid groups in the molecule, the said aqueous solution having an initial pH of between 2.8 and 4.9.

17. A process as claimed in claim 16 wherein the dye bath additionally contains a dyestufi containing less than two sulfonic acid groups in the molecule.

18. A process as claimed in claim 16 wherein the dye bath is free from Glaubers salt and the initial pH is between 3.4 and 4.5.

19. A process as claimed in claim 16 wherein the dye bath additionally contains a dyestutf containing less than two sulfonic acid groups in the molecule and is free from Glauber's salt. 7

20. A process as claimed in claim 16 wherein said normal wool is treated with at least one of said aliphatic acid and said condensation product prior to being dyed with said dyestufi.

References Cited in the file of this patent UNITED STATES PATENTS Journal Soc. Dyers and Journal of the Society ary 1946, pp. 47-52.

Col., June 1945, pp. 144-150. of Dyers and Colorists, Febru-

Claims

1. A PROCESS FOR NON-UNIFORMLY DYEING A WOOL TEXTILE MATERIAL WHOSE WOOL CONTENT CONSISTS SUBSTANTIALLY ENTIRELY OF NORMAL WOOL FIBERS WHICH COMPRISES TREATING SAID TEXTILE MATERIAL, IN THE ABSENNCE OF CHLORINATED WOOL AND OTHER FORMS OF WOOL TREATED TO ALTER THE DYESTUFF AFFINITY THEREOF AS COMPARED TO NORMAL WOOL, WITH AN AQUEOUS SOLUTION CONTAINING A CONDENSATION PRODUCT WHICH RENDERS SOME OF THE AMINO ACIDS PRESENT IN WOOL AT LEAST PARTIALLY RESISTANT TO DYEING WITH DYESTUFFS WHICH NORMALLY DYE WOOL, SAID CONDENSATION PRODUCT BEING SELECTED FROM THE GROUP CONSISTING OF CONDENSATION PRODUCTS OF ALDEHYDES AND AROMATIC SULPHONIC ACIDS AND WATER-SOLUBLE SALTS OF CONDENSATION PRODUCTS OF ALDHEYDES AND AROMATIC SULPHONIC ACIDS, A WATER-SOLUBLE ORGANIC ALIPHATIC ACID WHICH IS NON-INJURIUOS TO WOOL AND AT LEAST ONE DYESTUFF WHICH WILL DYE WOOL AND WHICH CONTAINS AT LEAST TWO SULPHONIC ACID GROUPS IN THE MOLECULE, THE SA ID AQUEOUS SOLUTION HAVING AN INITIAL PH OF BETWEEN 2.8AND 4.9.