Mechanism of Dyeing and Dyeing

Auxiliaries

March 31/2016
Addis Ababa
 Dye fixation mechanism

Dye type Electrostatic Covalent H-bonded Hydrophobic

Acid P S
Basic S S S
Direct S P
1:1 premetallized S P
1:2 premetallized S S S
Reactive S P S
Sulfur P

P= Primary mechanism
S= Secondary mechanism
 Role of Iso electric point (IEP)

• IEP is the point on the pH scale at which the net charge on the
protein is zero
• In acidic media,
– P-CO2H + H3N+-P
– The net charge is positive or cationic
• In alkaline media,
– P-CO2- + H2N-P
– The net charge is negative or anionic
• At IEP,
– P-CO2- … H3N+-P
– The net charge is zero
 Role of Iso electric point (IEP)

• Two points on IEP,

– IEP does not change with changing pH
– IEP can only be changed if there is a chemical change that
alters the availability of active groups; this can occur in the
beamhouse processes, in the tanning processes and in the
post tanning processes.
Role of Iso electric point (IEP)
Changes of the IEP in leather processing
 Role of Iso electric point (IEP)

• In post tanning is that the IEP will gradually move down, from
pH 7 to pH 5–6
• Therefore, at any given pH, the leather will be less positive or
more negatively charged than it was before
• In other words, the leather has less and less affinity for anionic
reagents, so penetration of these reagents is favored.
 Role of Iso electric point (IEP)
• Estimated changes in IEP, starting with chrome
tanned leather at 7.0, then retanning, dyeing (1 : 1
premetallized dye, acid dye or reactive dye) and
fatliquoring.
 Role of the Sulfonate Group

• Leather chemicals that typically carry sulfonate groups include:

– syntans;
– modified vegetable tannins;
– dyes: acid, basic, direct, premetallized, reactive;
– fatliquors: sulfated fatliquors included.
• In each case, the mechanism of fixation is the same.
• An electrostatic reaction can take place between the anionic
sulfonate group and the protonated amino group.
• This can only happen when the collagen is acidified, to create
the cationic group.
 Role of the Sulfonate Group

• Above the IEP, there are no cationic centers for reaction.

• At the IEP, the cationic groups are locked together with the
anionic carboxyl groups
• By acidification that reaction with sulfonate can occur.
• The carboxyl groups are not in competition with the sulfonate
groups, because the weak carboxylic acid groups become
protonated
Mechanism of sulfonate fixation on collagen
 Dyeing auxiliaries

• Dyeing auxiliaries are leveling agents, penetrating agents,

intensifying agents and fixing agents
• They include:
– Anionic Auxiliaries
– Auxiliaries that Complex with Dyestuff
– Auxiliaries that have Affinity for both Leather and Dye
– Intensifying Agents
– Cationic Tannages
– Cationic Auxiliaries
 Anionic auxiliaries

• These are leveling agents is based on low molecular weight, aromatic

sulfonate condensates

For leveling, the degree of polymerization

may be 2–10.
 Anionic auxiliaries

• They function by competing with dyestuff for binding sites or

occupy those sites by prior treatment.
• Any reduction in availability of reaction sites reduces the rate
of interaction with substrate, making it more uniform.
• The auxiliary is added before the dye, the colour intensity may
be reduced by up to one-third of what would be obtained on
untreated leather.
• The effect of the auxiliary is enhanced at higher temperature,
e.g. 70 oC is better than 20 oC.
 Auxiliaries that Complex with Dyestuff

• These auxiliaries change the HHB/HLB properties and reduce

the anionic charge.
• Examples include polyglycol ethers with weakly cationic
amino groups.
• These will form strong complexes with high affinity dyes, to
improve penetration and levelness.
 Auxiliaries that have Affinity for both
Leather and Dye
• Examples include poly(ethylene oxide) chains with strong
cationic groups.
• These agents cannot be used with premetallized dyes
containing anionic dispersing agents.
• They tend to produce very pale colours when offered at low
levels.
• At higher offers, colour intensity can be increased or enhanced
 Intensifying Agents

• The purpose of colour intensifying agents is to allow dyes to

accumulate at higher concentration on the surface of the
leather.
• In this way, deeper shades are obtained
• These auxiliaries may also be referred to as dye fixing agents,
since their function is to create additional sites at which dye
molecules can be chemically bound to the leather, rather than
physically bound to it.
 Cationic Tannages

• The presence of cationic centers from the tanning reaction

provides addition sites with which anionic dye can react.
• Such tannages include Al(III) chloride or sulfate, Zr(IV)
sulfate, polyurethane and dicyandiamide retanning resins.
 Cationic Auxiliaries

• This class of auxiliaries includes cationic polyamine

compounds with nonionic ethylene oxide chains

• Other fixing agents are based on polyamines, such as

dicyandiamide derivatives