The dyeing and printing of silk fabrics

KYChu+ andJRProvost
+ ICI (China) Ltd, Great Eagle Centre - 16 Roor, P 0 Box 107, Hong Kong
ICI plc, Organics Division, Hexagon House, Blackley, Manchester M9 3DA

W t h the recent increase in the printing o f natural jibres, silk, the queen of fibres is again increasing in popularity. Apart from the traditional indusby o f printing scarves, ties and evening gowns there is an increasing trend o f more silk in the boung fashion areas. Dyers and printers of silk have, for obvious reasons, kept their know how, based on many years of experience, secret and little information on the practical processing o f silk has appeared in the technical litemture. The present paper will attempt to reuiew the prepamtion, dyeing and printing o f silk based on our experiences in the laboratory,pilot plant and in some cases on practical mill expenence.

1. INIRODUCllON Silk fabric, because o f its relative rarity, its unique lustre, softness and drape has over thousands o f years been considered the most valuable and prized fibre available. Recent fashion trends have switched very much to the naturalscene which has resulted again in an increase in demand for silk fabrics, particularly printed articles. Exact estimates of printed silk are difficult to give but figures in the region o f 150 million square metres are of the right order. Cornpared with other fibres discharge printing holds a far higher share o f the production (in the region o f 5040%). Table 1gives a breakdown o f the production o f raw silk (Bombyx f the Mori) over the last fifty years. The present importance o Peoples Republic o f China can be clearly seen, together with the relative decline o f Japan as supplier o f raw silk from 1938 to the f the PRC to the European silk industry present. The importance o can be seen from Table 2 where 90% o f the raw silk imported into W Europe comes from the PRC, the major user being the Italian f imports) [ 1 1 (seeTable 3). industry ( 80%o

2. COMPOSITION OF S M Silk, like wool is a protein fibre but contains some significant differences in its composition, part~cularly the absence o f sulphur (cystine f the physical and chemical nature o f links).A detailed comparison o silk fibroin and wool keratin has been given by Asquith 121. An approximate indication o f the chemical differences between them is given below:
Wool keratin Silk fibroin

Amino acids (non-polar) Basic side chains Acidic side chains W O Y l goups Sulphur groups

5 % 34 10
24

77 3.4

2.7
17 0.3

22
10

Morphologically silk consists o f two single endless filaments surrounded by silk gum (orsericin).The silk gum normally accounts for up to 25% by weight o f the raw silk.

TABLE 1 Raw sllk production (Bombyx Mod) (in OOO tonnes) (Roduction figure ex Intenrational Silk Assodation)
Major Countries 1938 4.8 1.8 0.7 43.1 1.9 4.2 56.5 1978
1.1 19.0 4.3 3.5 16.0 0.7 4.0 1.6 50.2

3 .FABRIC PREPARAnON
Raw silk possesses none o f the lustre or softness that is normally associated with silk. The supple handle appears only after the prepf the raw silk is generally aration stage is completed - scouring o referred to as degumming(or in some cases boiling-off1. Depending on the degree o f degumming a weight l o s s up to 25% can be expected together with a strength l o s so f 20%. The l o s so f weight and volume can be compensated for by subsequent weighting treatments using metal salt solutions. However, with printing processes a weighting treatment is rarely given as weighted silk can suffer fibre damage during the steaming process. f the delicate nature o f silk and the well-known probBecause o lems o f mechanical damage (chafing,pilling, etc.) silk is treated with extreme care (almost loving care) throughout all the wet processing stages. This is particularlytrue with the degumming stage which generally requires extremely long process times. Degumming methods have changed little over the years and the use o f starframes immersed in tanks or older home-made methods where individual pieces are folded in book-form and suspended by one selvedge into the degumming bath are still popular. A number o f the earlier tactbooks e.g. [3,41 are still very relevant to the subject. Continuous degumming ranges are now being offered by M a m a - Kleinewefers SpA [51 and a number o f units have been installed in the Far East. Dependent on the degree o f degumming three classes o f silk have been defined: 1. EcruSilk (Bast Silk) - Barely degummed (maximum 4% loss) - only removes grease, wax, and resin substances 2. Half-boiled Silk (Matt Silk) - The degumming loss is approximately 612% - the finished silk still retains approximately half the sericin

1980 1.2 23.5 3.2 4.7 16.1 0.7 4.3 1.8 55.5

1981 1.3 26.0 2.5 4.7 14.8 0.7 4.3 1.7 56.1

1982 26.0 5.0 12.6 0.7 4.3 1.7

Brazil
PRC

South Korea India Japan Thailand USSR

other

Total excludesTussah Silk

54.0

** 1982 figures are estimates

TABLE 2 Raw sllk imports W Europe [11 (in tonnes)

Year
1969 1975 1983

Jam

PRC
3096

Korea
114 12

Brazil
138 420 108

Other

Total

24

2309
4440

162 120 72

3534
2861 4620

TABLE 3 Raw sllk imports to major W European centres [ 11

Tonnes
Italy France Switzerland United Kingdom W Germany

(96)
79 14 3 2 2

3636 642 150 102

90
4620

REV. PROG. COLORATION VOL.17 1987 23

3. Cuite S i l k (Lustre Silk) -Completely degummed silk with a soft handle and a high lustre. The degumming process can include some o f the following sequences: Prelirninoy Sooking - Raw silk is soaked for 1 hour at W C ,then overnight in a cooling bath with 2 pts/lOOO sodium carbonate. Degumrning Proper - Either a one bath or in some cases a two bath method may be employed. (i) One Both Method: treatment for 2-3 hours at 9&95C in a bath containing: 10 pt/ lo00 soap (olive oil type) 0.5 pt/lOOO sodium carbonate or 1 m1/1000 ammonia (36Tw) (ii) Two Both Method: treatment as one bath method - reduce time to 1-2 hours followed by treatment for 1 hour at 90-95c in a fresh bath containing: 5 pts/lOOO soap (olive oil type) 0.3-0.5 pt/loOO sodium carbonate The treatments in either the one or two bath methods are followed by a mild alkaline rinse (1 pt/lOOO sodium carbonate) at W C and a final rinse with warm soft water. The use o f soap in an alkaline medium, rather than a synthetic detergent, particularly the green olive pulp or Marseillessoap, has been the standard method for many years. The use of synthetic degumming agents has been studied [6] and f reducing the processing time in degumpromoted [71 as a means o ming and consequently reduce the incidence o f silk lice formation (pitting) [81. Their use appears limited at the present. f the degumming process can be checked with The efficiency o f degumming can also use of the Pauly Reagent [7,91. The degree o be checked by the use o f C . I . Direct Blue 22 which will dye the sericin but not the fibroin. Bleaching of cultivated silk is normally carried out only for palemedium dyeings/prints and whites; for h e a y shades particularly for discharge grounds the bleaching stage can be eliminated. With tussah silks (wild silk) a full white can never be achieved, at best the natural brown colour can be bleached to a pale yellow. A typical process would be a treatment for 2-4 hours at a temperature o f 70C in a bath containing, 3 g/lo00 Sodium pyrophosphate 1g/lOOO Ethylene diamine tetra acetic acid (30% soh) 13 ml/litre Hydrogen peroxide (35% wt/wt soh) followed by a thorough rinsing stage. 4. DYEING OF S I L K Silk can be dyed by the typical dye classes used for the dyeing o f wool, viz, (i) acid dyes (ii) metal complex dyes and (iii) reactive dyes For discharge printing ground shades are normally selected from acid and premetallised dyes. However, one dye manufacturer has released a pattern leaflet advocating vinyl sulphone reactive dyes for the ground shades and vat dyes as the illuminants [lo]. A brief outline o f typical dyeing methods for the above dye classes is given below.

TABLE 4

Dyelng of e l k dyeing recipes for acid and pre-metallised dyes

Recipe Unisoi BT
Selected acid dye

5
(%)

(%I

2
X

(%I
2
X

(%I
2
X

(%I
2
X

2
X

Ammonium sulphate Acetic acid (30%) Glauber salt h P

2
4-6

C d i I
1

(dl)
2

5-15

45-60 min

/
Auxiliaries 30C

1 45-60 min

8 5 for ~ methods l.3and4

70cfor
methods 2 and 5

A J y i n /

Figure 1- Generol procedures for o d d ond pre-rnetallised dyes on silk Method 1 - is the best general dyeing method for silk fabrics in winch, overflow machines or on a jig. For difficult fabrics (i.e.delicate fabrics which are prone to creasing and chafing) the dyeing temperature could be lowered to 70-75C with only a slight loss in colour yield. Methods 2.5 - are recommended for dyes that are not exhausted well under the conditions o f Method 1. However the lower pH used and the presence o f Glauber salt could enhance the incidence of surface chafing when dyeing silk fabrics o f rough surface structure. Methods 3,4 - these dyeing methods are still popular in some factories in the Far East. However, the addition o f soap as a levelling f dyes that are suitable. Methods 3,4 are agent limits the number o not generally recommended. Overall, the best dyeing method for silk fabrics is Method 1 followed by Methods 2 or 5. For silk yam any of these three methods is suitable. Table 5 gives a wide range o f suitable acid and pre-metallised dyes, together with recommended dyeing methods and discharge performance.

4.2 Dyeing with reactive dyes

Recently there has been increased interest in the application of reactive dyes on silk. Papers have appeared dealing with both the practical nature [ll-141 and the theoretical aspects [15-181 o f the f silk. The advantages with reactive dyes over acid dyes are dyeing o f bright shades with good fastness obvious in offering a wide range o properties. However, the acceptance of reactive dyes in those countties where discharge printing is popular has been limited due to the claimed inferior discharge properhes in certain shade areas. Research work on silk dyeing has indicated that silk combines with the reactive dyes in a chemical fixation mechanism [ 161 similar to that for cellulose (i.e. under alkaline conditions and through hydroxyl containing side chains, e.g. tyrosine). Typical dyeing procedures for dichlorottiazine reactive dyes (Procion MX dyes-ICI) are given in Figure 2. Dyeing methods for vinyl sulphone reactive dyes have been discussed by Puke [ 111. Liddiard [ 121 and Rohrer [ 191 have discussed the application o f z Bromoaqlamide reactive dyes to both cultivated and wild silk (tussah silk).

4.1 Acid and pre-metallid dyes Traditionally, acid and premetallised dyes have been dyed under mildiy acid conditions. In the past the concentrated soap solutions left after the degumming stage were used as an excellent natural f silk. However, these have been r e p levelling agent for the dyeing o laced by combinations o f synthetic levelling and penetrating agents. A series o f dyeing methods has recently been developed based on an efficient low temperature dye levelling and penetration assistant, Unisol BT. These dyeing methods are based on both extensive laboratoy work and practical mill experience in the Far East. Table 4 and Figure 1 give a summary o f the dyeing recipes and procedures.
24 REV. PROG. COLORATION VOL 17 1987

Soda ash 129 I1

15rninv40rnin

~ O C

Silk can be printed by all the dye classes discussed in section 4 but in general, with the exception of one or two countries, direct printing is normally carried out using acid and metal complex dyes. Triphe nyl methane (TPM) based acid dyes, which have very bright shades f 2-3), and poor fastness performance (light fastness in the order o have also traditionally been used. 5.1 Reactive dyes Reactive dyes offer improved wet fastness performance and short steaming times. A typical recipe for monochlorotriazine reactive dyes is as follows: (PtS) Dye (Monochlorotriazine readve type) Urea ManutexF (10% solution) (Kelco International Ltd) Matexil P-AL liquid (ICI) Matexil WA-KBN (ICI) Sodium bicarbonate Water to
X

Dye Salt(h) Salt(+)

30 rnin Soda ash (29 I) Glaubers Salt (10-40g I)

Figure 2 - General procedure for Rocion MX dyes on silk Washing-off procedure for Procion MX dyes: (i) Cold rinse with 0.5 g/1 Soda ash and 1.0 9/1 Calgon T - 10 min (ii) Soap at 60-7oC with Lenetol B conc. (0.2 g/l) for 10 min (iii) Rinse with 1 ml/l o f ammonia (25%) at W C for 15 min (iv) Cold rinse (v) Optional acid rinse with 1 gm/l acetic acid (30%)to improve fabric handle.

100 500
30 20 25
lo00

5. PRINTING OF SILK Printed silk has always formed a high proportion o f the total output o f the silk industry. Articles such as ties, head scarves and haute couture dresswear have traditionally been printed with a range o f designs and colourings. Generally, because of the exclusiveness o f the finished article and the incorporation o f dry cleaning labels little regard to fastness performance has been given. This lack o f fastness performance is particularly true with discharge styles, where the f illuminant dyes provides extremely poor fastness levels. range o

Matexil P-AL liquid - (mild oxidising agent - sodium nitrobenzene sulphonate) Matexil WA-KBN - (combined wetting and anti-foam agent - an aqueous emulsion o f sulphonated fish oil and pine oil) ManutexF (Kelco International Ltd) - typical low viscosity sodium alginate thickener. Suitable Procion P dyes (monochlorotriazine reactive dyes) for silk are available [20]. After printing the fabric is steamed under atmospheric conditions at 102Cfor 10-15 minutes. The wash-off sequence, preferably in open width form, should incorporate the follaving steps:

TABLE 5

Selected add and metal complsr dyes f o r dyeing silk

b
Coomassie Yellow R Neutrichrome Yellow S G R Nylomine Orange C-G Coomassie Scarlet R Coomassie Scarlet B Nylomine Red C-2B Carbolan Rubine 2 8 Nylomine Red C-G Nylomine Bordeaux C 3 B Neutrichrome Orange S-R Neutrichrome Red S-GN Milling Brill. Violet 2BR Carbolan Violet B Milling Brill. Blue 2BR Milling Brill. Blue 2J Carbolan Blue 2G Nylomine Blue C-BR Nylomine Blue C-B Coomassie Blue B Carbolan Green 5G Carbolan Green G Coomassie Nay C Neutrichrome Nay S-B Neutrichrome Brown S-GR Neutrichrome Brown S-2R Neutrichrome Grey SBG Coomassie Black BN Neuhichrome Black S 2 B
0 Suitable 0 Less suitable

C.I. Number (acid) C.I. Yellow 42 C.I. Yellow 121 C.I. Orange 67 C.I. Red 97 C.I. Red 111 C.I. Red 138 C.1. Red 129 C.I. Red 151 C.I. Red 119 C.I. Orange 144 C.I. Red 359 C.I.Violet 17 C.I.Violet 48 C.I. Blue 83 C.I. Blue 90 C.I. Blue 175 C.I. Blue 208 C.I. Blue 127:l C.I. Blue 80 C.I. Green 28 C.I. Green 27 C.I. Black 26 C.I. Blue 284 C.I. Brown 282 C.I. Brown 357 C.I. Black 188 C.I. Black 107

Dyeing Method 1 2 3 4 5

Dischargeability (C.I. Reducingagent2)

J + J J

5 + J +

$
J J J J + -

J + -

5 J

J + -

x Not suitable J Dischargeablewith C.I. Reducing agent 2 based recipes. However degree of white (and susceptibilityto subsequent darkening after exposure to light) m u s t be m i n e d in detail before processing in bulk + Small gamut o f dyes suitable a sb a s k for trichromats - Suscqtibilityto darkeningafter prolonged exposure to light

REV. PROG. COLORATIONVOL. 17 1987 25

(i) cold rinse (ii) rinse for 5 minutes in water at W C (iii) treat for 10 minutes at W C in solution containing 2 pts/1o00

Lenetol B (ICI - a nonionic ethoxylated fatty alcohol detergent), 1pt/lo00 Soda ash (iv) rinse in a solution containing 2 pts/lo00 Matexil FC-PN (ICI a cationic fixing agent) acidified with acetic acid. and (v) the fabric is dried without further rinsing.

as possible and normally consists only of a thorough rinse in cold water (20C) using copious amounts o f water, followed by a warm rinse with 1 pt/lOOO o f Lenetol B at 30C and a final rinse in cold f the deliwater containing 5 pts/lo00 Matexil FC-PN. Because o cate nature and poor standard o f fastness o f the brighter TPM dyes many printers make do with a cold rinse stage until the unfixed dye is removed and then give a subsequent dye fixing treatment with Matexil FC-PN.
6. DISCHARGE PRDITING OF SILK The discharge printing o f silk is one area where little technical knowledge has been published. Specialist discharge printers o f this style are found in Italy, France, W Germany and UK in Europe and the Peoples Republic o f China, S Korea, Japan, Thailand and India in the Far East although many designers / students etc. attempt to produce lengths for their collections. Detailed method are rarely published either by the printer (for obvious reasons) or by the dyestuff manufacturers. This section will give an outline o f the major processing methods and highlight the essential points that printers new to this style should heed in order to achieve satisfactory discharge prints on silk. As with all discharge printing a considerable amount o f process development will be required by the printer under his own conditions.
6.1 Dye selection f o r ground shades Table 5 gives a range o f selected acid and metal complex dyes that can be discharged at a 1/1 standard depth using C.I. Reducing Agent 2. However, no absolute statement can ever be made that a particular dye is dischargeable to a satisfactoty white due to the many factors that can affect the dischargeability, for example: (i) particular acid or metal complex dye selected (ii) the depth o f shade used (iii) whether the dyes used in a particular combination have similar discharge performance (it only requiries one dye o f a combination dyeing to leave a small residual stain to affect the acceptability o f the white) (iv) susceptibility o f a particular dye (or combination)to darken(reoxidise) on exposure to light. This is particularly true with TPM (biphenyl methane) acid dyes. (v) type and concentration o f reducing agent used and (vi)print auxiliaries used in recipe, The resultant discharge can also be affected by the mechanical f parameters involved in the printing which govern the amount o colour paste applied, the degree o f colour paste penetration and the final removal o f the dye discharge products. Particular mechanical aspects which can effect the final discharge include: (i) printing method (hand screen methods can apply more print paste than an automatic flat screen machine) (ii) printing screen mesh selected (iii) drying method f processing (iv) fixation equipment and time o and (v) efficiency of washingoff equipment It is therefore vital to cany out initial trials on the selected dye at a range of depths using the print recipe and equipment to be used in bulk. Popular dye combinations should also be m i n e d in the same manner. Grounds, are, in general, based on selected acid and metal complex dyes. Reactive dyes can be used and have been advocated [ 10, 111but their use in general is extremely limited in the main centres o f discharge printing. Dyeing methods for ground shades have been discussed in Section 4.1. A popular combination o f dyes used in practice in the main discharge markets are: Coomassie Yellow R (ICI)- C.I. Acid Yellow 42 Coomassie Scarlet B (ICI)- C.I. Acid Red 111or Coomassie Scarlet R ( I C I ) - C.I. Acid Red 97 Coomassie N a y C (ICI)- C.I. Acid Black 26 supplemented by Milling Brilliant Blue 2J (ICI - C.I. Acid Blue 90) when bright blues are required. (Note thii TPM dye darkens on exposure to light.)

5.2 Acid and metal-complex dye8 These are the most widely used group for the duect printing of silk fabrics. Italy, the largest market for silk in W Europe (Table 31, uses these dyes almost exclusively for all outlets.A typical recipe is as follows: (Pts) X Acid or Metal complex dye Thiodiglycol 40 Unisol BT (ICI) 10 Urea 30 Hot water Y Thickener 500 Acid generator (1:3 solution) 90
Water to

lo00

Thickening agents used by printers tend to be combinations built up from proprietay products. Typical products used as a basis are crystal gum, British gum, guar gum or tamarind based gurn. Many printers in Italy still use British gum, which has long disappeared from the UK,normally in admixture with guar based products. As acid generators, ammonium tartrate and ammonium oxalate are popular. Ammonium sulphate, which is sometimes recommended, can cause yellowing o f the printed area under certain drying conditions when thickeners based on guar gurn are used and should therefore be avoided. Typical acid and premetallised dyes used in f silk have been listed previously (211. Where brightness o f printing o shade is important these can be supplemented by a number o f triphenyl methane based acid dyes which have, however, poor fastness performance, e.g. C.1. Acid Red 52, C.I. Acid Violet 17, C.I. Acid Blue 83 and C.I. Acid Blue 90.

5.2.1hinting conditions Printing of silk is normally carried out on hand screen tables, semiautomatic flat screen machines (e.g. Galli S A types)or automatic flat machines. For good printing results the normal printing para meters of (i) screen mesh, (ii) squeegee type and pressure used, (iii) printing f squeegee strokes and (v) drylng conditions viscosity, (iv) number o must be optimised for particular fabrics, designs and print machines. Normally, screen meshes are extremely fine for silk printing - 25 T f 186/inch (or (silk gauze number) corresponding to a mesh count o 73/cm) is used although for particularly fine work even finer meshes are used [22]. With hand tables the use o f those tables having some form of heating incorporated into the table is recommended (e.g. steam-heated hand tables are popular in the Far East). It is also f overhead hot air drylng, such as recommended that some form o hot air ducts, is used. Prolonged air drying (via the normal hanging methods) should be avoided particularly for printers based in tropical countries. With automatic screen printing machines an efficient and controllable drier is normally available although some printers also incorporate an extra hot air drying system (by blowing hot air directly onto the printing blanket) at various positions along the print blanket.
5.2.2Steaming and washing Steaming is nomally carried out under atmospheric conditions (102C)for 30-45 minutes in a festoon steamer or a star pressure steamer (not operating under pressure). Washing-off must be carried out under tensionless conditions as far
26 REV. PROG. COLORATIONVOL 17 1987

Also, a specific mixture acid milling dye, Coomassie Black BN (ICI)

- a mixture black specifically developed as an economic dischargeable black for silk, is popular in discharge printing markets.

6.2 Rinting stage

Reducing agents are used exclusively for the discharge printing of silk. Resist methods, which have been developed for other substrates (e.g. polyester [23]) in order to eliminate the need for reducing agents with all their inherent stability problems, have not proved acceptable to the printers of this style. Reducing agents used are normally based on formaldehyde stabia l t s of sulphoxylic acid. Stannous chloride can be used lid s although the number o f suitable grounds are restricted and today is rarely used. Thiourea dioxide (formamidine sulphinic acid) - C.I. Reducing Agent 11although advocated is also not used. In practice printers use: C.I. Reducing Agent 2 - sodium formaldehyde sulphoxylate (C\OHSO$la) either alone or in combina tion with the insoluble calcium salt - C.I. Reducing Agent 12 calcium formaldehyde sulphoxylate -an insoluble form. When used in combination with the sodium salt it gives much improved definition and a Iowa incidence o f haloing. f C.I. Reducing Agent 12 - Rongalite A 30% aqueous dispersion o H liquid (BASF) has been introduced which overcomes the problems associated with the insolubility o f C.I. Reducing Agent 12 - viz. screen blockages etc. A recent development from Italy has been the introduction o f special formulation containing C.I. Reducing Agent 12 from Industria Chemica lngredienti Tessili o f Milan. This new product Rodanil is proving popular with Italian silk discharge printers. Currently, the majority o f W European discharge printers (particularly Italian printers) are using either mixtures o f C.I. Reducing Agents 2 and 12 or C.I. Reducing Agent 12 alone. C.I. Reducing Agent 6 - zinc formaldehyde sulphoxylate - although popular for wool discharge printing, its discharge performance is inferior to those of C.I. Reducing Agents 2 or 12 (or combinations of these two).C . I . Reducing Agent 6 is rarely used in West Europe, although it is used by some printers in Hong Kong and the Peoples Republic of China (in the Shanghai area). f work has been carried out on the mechaA considerable amount o nism of the decomposition o f sodium formaldehyde sulphoxylate when used in discharge printing. A much simplified mechanism is given below: (i) decomposition o f the agent: CH,OH SO,Na -+ CYOH SOYa + 2H 1t N a p , HCHO + N%SO, + CO, (ii) destruction of the azo link in dyed ground Ar-N = N - Ar + 4H + ArNH, + ArNH, 4re Decomposition products (amines)

Note 1 - Hydrotrope agent, amount depends on the dye to be discharged and the steaming equipment. For the older festoon steamer or star steamer urea can be omitted. Urea is not normally found in the illuminant recipes. Note 2 - Hydrotrope agent comments as above. Unisol BT also assists in solubilisationo f the illuminant dye. f sodium and calcium formalNote 3 - Normally a combination o dehyde sulphoxylate - amounts obviously depend on depth o f ground shade. Note 4 - Thickening agents are normally based on galactomannans either used alone or in combination with starch based products (e.g. British gum is still a popular component in a thickener mixture used by Italian printers). Particular blends available from the thickener manufacturers include: Indalca M747 (Hercules plc) M ~ ~ I J INF-16 T I (Mehyall AG) Guaranate GC/250 (SFC) (limberti SPA) Rintex PS/14 Polyprint S-240 LV (PolygalAG) Note 5 - Zinc oxide (normally a 1/1 paste) gives an improved white and also acts as a buffer preventing fibre degradation. Note 6 - Some printers recipes include a mild oxidising agent e.g. Matexil P-AL (ICI- sodium m-nitrobenzene sulphonate), sodium chlorate or sodium nitrite in the illuminant recipe in order to improve print paste stability. Note 7 - Some printers also incorporate an FWA which is stable to the reducing agent. The range o f illuminants stable to reducing agents such as C.I. Reducing Agents 2 and 12 is extremely small and many o f those dyes suitable have extremely poor light fastness (figuresas low as 12) and effect changes in an I S 0 1 wash test o f 2. Table 6 gives a small range of dyes which are stable to the reducing agent normally used. Some specialist firms, in markets where discharge printing of silk is popular, use this small gamut o f available illuminant dyes and mix a full range o f illuminant dyes (e.9. Rota SpA o f Italy).

TABLE 6 Dyes suitable as illuminants In silk diechargeprinting

4res
C . I . Direct Yellow 28 C . I . Acid Red 52 C . I . Acid Red 87 C.I.Acid Red 195 C . I . Acid V i o l e t 90 C.I. Basic Blue 3 C.I. Reactive Blue 198 C.I. Direct Blue 106 C.I. Acid Black 2

Examples

4.0

S o l a r Yellow ffi (S) Sulfacide Brill. Pink 3 B ( I C I ) Eosine DA ( I C I ) Neolan Pink BE (CGY) Neubichrome Bordeaux M-B (ICI) Yoracyl Blue 5G (YCL) Rocion Blue H-EGN (ICI) Diazo1 Light Blue 2 F WL( I C I ) Nigrosine G140 ( I C I )

6.2.1. Print recipes The following components are normally found in typical discharge recipes:
White (Pts) urea Thiodiglyol Unisol BT (ICI) Reducing Agent Thickener Zinc oxide Stability improvement agents Fluorescent whitening agents Water to (Note 1) (Note 2) (Note 2) (Note 3) (Note 4) (Note 5) (Note 6) (Note 7) Coloured (Illuminant) (Pts)

&50 10-30

10-30 10 50-150 50-150 500600 500600 50 Pts 0-20 0-10

lo00 lo00

6.2.2. Printing method Due to the small lengths printed, the printing methods are normally confined to hand screen, semi-automatictables (e.9.Galli S A types) or automatic flat bed machines. The normal screen printing parameters, screen mesh, squeegee pressure, printing viscosity and type and number o f squeegee strokes, have to be adjusted for a particular design and a specific fabric. W i t h hand tables the use of those tables having some form of heating into the table is recommended (eg. steam or elecbically heated). It is also common to find some form o f overhead heating in order to assist drying between screens. 6.2.3. Post printing operations Steaming is normally carried out under atmospheric conditions for 5-20 min in a star steamer or a more normal festkn steamer. With an efficient steamer initial trials should concentrate on short steaming times (5-10min) as prolonged steaming, besides giving rise to halos, can reduce the illuminant colour yield. Washing-off should be carried out using mild conditions, in open
REV. PROG. COLORATION VOL 17 1987 27

width if possible, with a good exchange of liquor in the initial cold rinsing stage as follows. (i) rinsing cold - C.I. Basic Blue 3 normally requires a longer rinsing stage than other illuminant dyes (ii) mild soaping - mild soap with 1pt/lOOO Lenetol B at 3 W C (iii) cold rinsing (iv) after keatment with a cationic dye fixing agent (e.g. 5 pts/lOOO Matexil FC-PN). f silk discharge prints i s normally restricted to The final finishing o either a scrooping or softening stage. Scrooping is carried out using lactic acid (10pts/lOOO) for 5-10 min in the cold followed by drying. As the final handle o f silk is an all important selling feature the softening (chemical),anti-creaseor elastomeric finishes (increasing in popularity) on silk tend to be closely guarded process secrets o f the dyer or printer and little detailed information has been published.

3.J T Marsh, An Introduction to Textile Bleaching (London: Chapman & Hall, 1951)371.
4. C M Whlttaker. C C Wlkodc, Dyeing with Coal-Tar Dyesluffs, (Ballliere.Tindall and Cox (1942) 40. 5.D H Wyles. in Engineering in Coloration(Bradford Dyen Co.Pub. Trust, 1985) Chapter 1. 6.S M Chattdi. Textile Manufacturer. June (1967). 7.K Mahall. Tsdlle Asla. October (1985) p95-101. 8.J Hilden, Int. Text. Bull.. 1st Quarter (1985) p41. 9.Remington. J. Textile Inst., 2 1 (1930) T237. 10. Hoechst A G. Pattern Leaflet DM001 D.

11. HPutze.TextiIRawls.39(1984) 1051.

12.ALlddlard,J.S.D.C..99(1983)56. 13.R R Shankarachary.Colourage,31 O c t h (1984) p33-35. 14.R Hofstetter, Textile Praxis,40 (1985) 1233. 15.Y Xia,J. S.D.C..99 (1985) 56. 16.P Ball, J Meyor,J Yang. H Zollinger. Textikedlung, 20 (1985) 68. 17.0Meyer. J Wang. Y Xla. JYang, H Zolllnger. J.S.D.C.. 102 (1986) 6. 18.B Vogt, U Altenhofen, H Zahn. Textilwredlurg. 20 (1985) 90. 19.R Rohrer, Textihwedlung.20 (1985) 85. 20.ICI pk. OrganlaDlvlslon. Technical Information Note D1484. 21.H Gutjahr in Textile Printing (Bradford D,w Co. Pub.Trust. 1981)~ 1 8 3 . 22.F Belde. Screen Gauzes in Textile Printing. Btyer Fatten Revue. No. 23. 1973.

REFERENCES
1. L Zosso, Textiberedlung,20 (1985) 78. 2.R S Asqulth, Chemlsby of Natural Protein Fibres. (New York: Plenum Press, 1977)53

p42-57. 3. 23.D Brlerley, J R Provost. J.S.D.C.. 99 (1983)

28 REV. PROG. COLORATIONVOL 17 1987