Space Dyeing (Naphthol Colors)

Using Single Naphthol Single Base

Undyed/light - dark dyed combination

Step 1:- Apply Naphthol to the entire material on roller dyeing machine. Do partial hydro extraction to remove excess naphthol.

Step 2 :-Devide the hank in 4 equal part and calculate the length of light/undyed part required in the folded hank.Set the water level in the machine upto the required undyed part ( just to dip the required length). Set the bath with acetic acid and soap at 85-90 0 C. Lower down the hanks in water , keep it for 10 min, The hanks will remain steady during this period. Lift the hanks and squeeze them manually to remove excess water other wise water will percolate down. The temperature and acid will remove the naphthol from this particular portion.

Step 3:-Rotate the hanks by half turn , so that washed portion go up and the opposite part comes to the right position. Repeat step 2 in the same bath.

Step 4:- Squeeze the material to remove excess water , the hanks will appear as in the fig. Make the base bath ready.

Step 5:- Run the entire material in the base bath as usual to develop the shade .The washed portion will remain white or lighter depending upon the effectiveness of washing , while the unwashed portion will develop fully.

Neutralise , soap and Rinse as usual.

Light and Dark Shade combination

Step 1:- Apply Naphthol to the entire material on roller dyeing machine. Do partial hydro extraction to remove excess naphthol.

Step 2 :-Devide the hank in 4 equal part and calculate the length of light part required in the folded hank.Set the water level in the machine upto the required undyed part ( just to dip the required length). Set the bath with cold water. Lower down the hanks in water , keep it for 10 min, The hanks will remain steady during this period. Lift the hanks and squeeze them manually to remove excess water other wise water will percolate down.The action of water will remove the naphthol from the dipped portion ,you can play with temperature for the desired depth.

Step 3:-Rotate the hanks by half turn , so that washed portion go up and the opposite part comes to the right position. Repeat step 2 in the same bath.

Step 4:- Squeeze the material to remove excess water , the hanks will appear as in the fig. Make the base bath ready.

Step 5:- Run the entire material in the base bath as usual to develop the shade .The washed portion will remain white or lighter depending upon the effectiveness of washing , while the unwashed portion will develop fully.

Neutralise , soap and Rinse as usual.

Contrast shade One naphthol - Two Bases

As we know that one naphthol can produce different tone when combined with different bases , this property of the azoics is exploited in this combination, different steps in this process are,

Step 1:- Apply Naphthol to the entire material on roller dyeing machine. Do partial hydro extraction to remove excess naphthol.

Step 2 :-Devide the hank in 4 equal part and calculate the length of light/undyed part required in the folded hank.Prepare the dye bath with the desired base and set the water level to desired height of first color. Lower down the hanks in water , keep it for 10-20  min,with manual stirring of the hanks but the hanks will remain steadly dipped in the developing bath during this period. Lift the hanks and squeeze them manually to remove excess base other wise base will percolate down.

Step 3:-Rotate the hanks by half turn , so that developed  portion go up and the opposite part comes to the right position. Repeat step 2 in the fresh or replenished developing bath.

Step 4:- Squeeze the material to remove base , the hanks will appear as in the fig. Make the base bath ready for the second shade.

Step 5:- Run the entire material in the base bath as usual to develop the shade .The already developed portion will remain as it is because there is no naphthol remained to react with fresh base , while the undeveloped portion will become the second color.

Neutralise , soap and Rinse as usual.

More contrast shades can be made by double dyeing method , such dyeing fully one shade , then applying fresh naphthol to the entire material and doing one method  any of  above three.

Note :- The calculations for base and chemicals are done the basis of approximate weight of the portion to be devloped.
Look for more Space dyeing with Vat Colors in Hank Form

Naphthols and Bases

Azoic Dyes (Naphthol Dyes)
Naphthol dyes are insoluble azo dyestuffs that are produced on the fiber by applying a Naphthol to the fiber and then combining it with a diazotized base or salt at a low temperature to produce an insoluble dye molecule within the fiber. Naphthol dyes are classified as fast dyes, usually slightly cheaper than Vat dyeings; the methods of application are complex and the range of colors limited.
Azoic combinations are still the only class of dye that can produce very deep orange, red, scarlet and Bordeaux shades of excellent light and washing fastness.The pigments produced have bright colors, and include navies and blacks, but there are no greens or bright blues. Crocking fastness varies with shades but washing fastness is equal to Vat dyeings, generally with less light fastness than the Vats.
Naphthols :-The Naphthols are phenols, soluble in alkaline solution and substantive to cotton, particularly in the presence of salt. The anilides of BON acid(beta-oxynaphthoic acid or BON acid) are soluble in dilute NaOH solution and form the corresponding naphtholate ion. These relatively small molecules are of only low to moderate substantivity for cotton, but they diffuse rapidly into the fibres. In general, the higher the substantivity the better the rubbing fastness as less azo pigment forms on the fibre surfaces. The naphtholate ions are always coplanar and preferably have elongated molecular structures. They behave essentially as colorless, low molecular weight direct dyes. The substantivity increases with increase in the molecular size of the naphtholate ion, but the diffusion rate in the fibres and solubility in dilute aqueous alkali decrease. Addition of salt promotes better exhaustion of the bath, more being needed for Naphtols of lower substantivity.
Bases:-These are available as the free amine base or as amine salts such as the hydrochloride.Many of the amines used are simple substituted aniline derivatives with no ionic substituents. The so-called Fast Colour Bases require diazotisation. This usually involves reaction of the primary aromatic amine in acidic solution or dispersion with sodium nitrite, at or below room temperature. Successful diazotisation requires careful weighing of all the chemicals and regard for the supplier’s recommendations. Diazotisation of a primary aromatic amine is often difficult and solutions of diazonium ions are inherently unstable. They undergo decomposition even at low temperature and particularly on exposure to light. Storing prepared diazonium ion solutions is not usually possible.
General Dyeing Procedure

The application of the naphthols is consists of following steps,
1.Dissolution of the naphthol component.
2.Exhaustion of the naphthol dolution onto the substrate or absorption of the naphtholate ion by the cotton;
3.Removal of excess naphthol from the material by squeezing, partial hydroextraction or brine washing.
4.Diazotization of the base component.
5.Development or treatment with the diazonium ion solution to bring about coupling.
6. Neutralisation ,Soaping at the boil to remove superficial pigment, followed by rinsing and drying.
The process can be carried out in almost any type of dyeing machine determined by the form of the goods.
Dyeing Methods

Precautions in Naphthol Dyeing

1.The alkalinity of the naphthol bath shall not drop below the prescribed limit , otherwise the naphthol may presipitate.

2.Formaldehyde shall not be used when working at more than 50 Deg C or when the material is to be dried after naphthol application.

3.Material shall be protected from water spotting,steam,acid and chlorine fumes , and exposure to sunlight after naphthol application.

4.Use of excess salt in naphthol bath may result into precipitation of the bath.

5.The temperature is very important in base preparation stem , otherwise diazotization may not take place.

6.Sodium acetate must be added to the developing bath just before the use , otherwise base will become unstable due to fall in concentration of HCl.

7.Hydroextraction time must not be too long , which may result into light spots after development.

8.Material shall be rinsed without delay after developing , otherwise the mechanically held excess developing liquor will undergo some decomposition and cause deposition of dark colored spots , which will be difficult to remove.

9.It is important to use sufficient amount of alkali binding agents , otherwise it will result into presipitation of developing bath.

Stripping of Faulty Dyeing

-Treat the dyed material with Non ionic detergent and 3-5 gpl caustic soda at boil for 15 min. cool to 85 degC

-Add 3-5% sod. hydrosulphite for 30-45 min at 85 deg.

-Rinse hot and cold

-Bleach with 1-2 Gpl Available chlorine for 20 min.

-Antichlore and neutralise.

-Soap at Boil for 15-20 min.

-Cold rinse.
Role of Different chemicals

T.R. oil :-Wetting agents for naphthol pasting and dissolution and penetrating agent in fiber in naphthol application.

Caustic Soda:-For solubilising of naphthols and keeping proper alkalinity of naphthol bath.

Formaldehyde:-Protective agent of naphthol impreganated material from effect of air.

Salt:-Electrolyte for exhaustion of naphthol during naphtholation and to prevent the desorption of naphthol in the bath during brine rinsing and development phase.

HCl acid:- Dissolution of base and to produce nitrous acid in diazotization phase.

Sodium Nitrite:- Producing nitrous acid in diazotization process.

Sodium Acetate:-For neutralization of excess HCl in developing bath.

Acetic Acid:-As an alkali binding agent in developing bath.

Non Ionic Dispersing agent:-To keep the azoic pigments in fine dispersion phase , which are formed by the coupling of free naphthol in developing bath. Also helps in better color fastness during soaping operation.

Fastness properties on cotton

Correctly prepared dyeings with azoic combinations on cotton have fastness properties often comparable, or only slightly inferior, to those produced using quinone vat dyes. They complement the vat dyes because of the wide range of orange, red and Bordeaux shades that they provide.
The fastness to washing of azoic combination dyeings on cotton is usually very good to excellent but only after careful elimination of particles of azo pigment loosely adhering to exposed fiber surfaces. Intermediate drying or rinsing of fabric containing the Naphtol, and the soaping of the final dyeing, are key processes ensuring optimum fastness. The same argument applies to rubbing fastness. Deep dyeing that have not been well soaped easily transfer color onto adjacent white fabric, even under conditions of gentle rubbing.
There are two other problems associated with the fastness properties of azoic combinations on cotton. In pale shades, the dyeings often have much reduced light fastness, particularly under humid conditions. Some sensitive azoic combinations also give dyeings of only fair resistance to chlorine and peroxide bleaching.

Vat vs Azoics

A.Azoics are economical than Vat dyes.

B.Bright reds , oranges and deep maroon shades are possible in Azoics.

C.Limited Shade range in Azoics.

D.Bright pinks , bright Blue . olive green , green and blacks are not possible in Naphthols.

E.No fear of photodegradation in Naphthols.

F.Rubbing na dlight fastness is inferior in Naphthol dyeing.

G.More Suitable for Tie-dye and space dyeing.

Reactive Vs Azoics

A.Limited shade range in Azoics.

B.Dyeing method is very complex with too many variables in naphtholation , diazotisation and developing baths.

C.Color fastness to Chlorine is better in naphthols.

D.rubbing and Light fastness are inferior in azoics.

E.Dark and bright reds , maroons and ornages can be produced in azoics which are difficult in reactives.

F.Azoics are suitable for Tie-dye and space dyeing.
Space dyeing and Tie dye with naphthol dyes