5-Buku-TFL Dyes - Dye-Auxiliary-Presentation-08 - Franz Wyss

Dyes & Dye Auxiliaries
Workshop 2008
2008, C. Page & F.Wyss 1
Copyright TFL Ledertechnik AG

Dyes & Dye Auxiliaries
Agenda
• Dyes
• Dye Auxiliaries
• FAQ
• Technical Know How Exchange
• Regional Range Definition
• Promotion Activities / Material
• Selling Strategy


What is colour ?
We can perceive
specific wavelengths as colours
Our eye can only see light energy

that falls within the 400 - 700 nanometres
wavelength range
IR
UV
400 nm 700 nm

What is colour ?
To see colour
we need a light reflected light
source

Why the same colour can look different ?
In order to evaluate colour,

the light source is very important
Under artificial light a colour appears more yellowish

Metamerism
The colour of an object depends on the

light source under which it is viewed.
If 2 objects have the same colour under one light

and appear different under another light
this phenomenon is called metamerism

Metamerism
Colour measurement results of a metameric dyeing
Spectral reflectance graph
artificial light
day light

How do we describe colours ?

How do we describe colours ?
A coulor is divided into the shade (hue),

brightness (chroma) and lightness (lightness)
shade brightness lightness

Can we measure colour ?

How can we measure colour ?
With the
internationally
accepted CIELab
system we define
colour using a 3
dimensional
colour space.

How can we measure colour ?
CIELab cross section
+ a* values represent red hues

- a* values represent green hues
+ b* values represent yellow hues
- b* values represent blue hues
The chroma (C*) is 0 for a purely

achromatic color and increases as
the color becomes more brilliant.
The lightness (L*) ranges between

0 = black and 100 = white

How can we measure CIELab values ?
The spectrophotometer measures the spectral

reflectance between 400 - 700 nm
in 10 nm wavelength steps

Computer Colour Matching
Computer colour matching technology helps quickly to respond
• to market trends (fashion)

• to customer needs (right shade)
• provides technological advances (in time to market)
What is needed ?
• shade sample
• calibration of each selected dye within a colour scale
(from pastel to full shade on a defined material)
• spectrophotometer (electronic eye)
• computer software (e.g. Data-Colour)
• dyeing equipment
• computer colour matching know how


Colouring Agent - Chemical Classification
O H
N
TiO2
N
Colouring Agent H O
Inorganic
Organic
Pigment N N
Dyes
Anthraquinone Dyes
Sulphur Dyes
Azo Dyes
others

Colouring Agent - Chemical classification
Azo dyes
other
azo dyes
Azo dyes are the largest group of synthetic dyes world-wide,

with approx. 75 % of the market
They contain one or more Azo groups as the chromophore
N N

Mono and Polyazo Dyes
Monoazo dye: only one Azo group
NN
Dis and polyazo dyes: 2 or more Azo groups
NN NN NN

NN NN NN

Mono and Polyazo Dyes
O
examples HO HN CH3
N N
HO3S SO3H
Acid Red 1
HO NH2 HO
N N N N N N N NH2
H
HO3S SO3H HO3S
Direct Black 168

Metal Complex Dyes
NN NN NN
M M M
H2 H2
H2 NN NN
O O
O
1:1 complex 1:2 symmetric 1:2 asymmetric
Metal complex dyes are also Azo dyes !

Form of Dye Molecules
Different sizes and shapes of dye molecules results

in different dyeing behaviour
NN NN
Mono-azo (red, yellow)

Cr
NN
NN NN NN
Poly-azo (brown, black) Metal complex

(many colours)

Dyes - Definition and Classification
Organic Dyes - Classification

(Colour Index)
Acid
Direct
Reactive
Sulphur
Mordant
... Basic, Disperse, etc.

Acid Dyes (majority of leather dyes)
+ wide range of different colours

+ good affinity to leather
+ in general good fastness properties
+ respond well to cationic auxiliaries
+ bigger molecules gives more intense colour
+ smaller molecules penetrates better
- difficult to select compatible dyes

- large variation of dye behaviour
- needs a lot of dye experience

Direct Dyes
+ high light fastness

+ good fastness to migration
+ good wet and dry cleaning fastness
+ gives brilliant shades on cationic charged leather
+/- moderate penetration

+/- moderate solubility  less levelling
- poor compatibility with other dye classes

Sulphur Dyes
+ very good penetration

+ very good wet and dry cleaning fastness
+ good light fastness
+ good fastness to migration
- very poor build up

- dull shades

Reactive Dyes
+ wide colour range

+ in general good levelling
+ very good wet fastness when used at high pH
- poor colour build up

- high manufacturing costs (expensive dyes)
- difficult to fix below 60°C

Mordant Dyes
+ very good penetration
+/- not used as single dye
- poor build up
- poor fixation

TFL SELLA® Dyes Classification
Acid Dyes 95% of TFL SELLA® dyes
Direct Dyes SELLA® FAST Yellow R, Scarlet L, Red E, Blue L,

Blue 4GL, Turquoise 2BL, Violet RL, Black FS
Sulphur Dyes SELLAFLOR® Black P-S conc
Reactive Dyes component of SELLA® FAST Red 2B
Mordant Dyes component of SELLA® STAR dyes
All other dye classifications are not present in the TFL dye range

Properties of Leather Dyes
Shade (nuance)
Penetration
Colour Build-Up
Compatibility
Fastness Properties
light fastness
perspiration, washing, dry cleaning
fastness to migration (PVC, finishing coat)

Penetration: Build-up:
small dye molecules large dye molecules

round form linear form
many sulfonate groups less sulfonate groups
Penetration and build up are also strongly dependant on the

anionic / cationic character of leather, the application method,
the amount of dyes and dye auxiliaries used.

Examples
TFL dyes with very TFL dyes with very

good penetration: good build up:
SELLAFLOR P range Almost all SELLA FAST Colours

SELLA STAR range SELLA FAST Black conc type
SELLA FAST Brown HH 150% SELLA FAST Brown C-G
SELLA FAST Brown HG SELLA FAST Brown HC
SELLA FAST Brown HE 130% SELLA FAST Brown DZ 150%
SELLA FAST Grey A SELLA FAST Grey C-LL
A complete list is available in TFLnet

Light Fastness
Light Fastness Test on Blue Scale (Xenon)
20h 80h
Scale 1 - 8

Fastness to Migration
Migration Test on PVC

Perspiration Fastness
Perspiration Test on Wool and Cotton

One dye - different properties ??
Example: Shade and migration fastness of Acid Brown 75

from different producers
3
4-5

One dye - different properties ??
HPLC chromatogram
A BR 75
Manufacturer 1
Migration fastness: 2
A BR 75
Manufacturer 2
Migration fastness: 4-5

How can we influence the properties on leather ?
Select the right dyes to achieve the requested

properties (penetration, build up, fastness etc.)
Select suitable chemicals (retanning, fatliquoring)
Make use of dye penetration, build up, levelling and

fixing agents
Work out the best suitable recipe (temperature, time,

float length, dyeing process (e.g. before or after retanning),
etc.)


Dye Auxiliaries - Definition and Classification
Why do we need dye auxiliaries?
- to level out imperfections (levelling & dispersing agents)

 in leather
 between dyes
- for improved and even dye penetration (levelling & dispersing agents)
- to improve shade intensity (shade deepening agents)
- to improve dye fixation (dye fixing agents)
To achieve levelness & shade consistency, good and even penetration, good dye fixation
without auxiliaries
dyes must have a similar charge density, compatible behaviour and good fixing properties

Dye Auxiliaries - Definition and Classification
TFL has 3 categories of dye auxiliaries
Levelling and dispersing agents

INVADERM® LU / RA SELLASOL® TN gran
INVADERM® AL INVADERM® B SELLASOL® TN-FF liq
Shade deepening agents

INVADERM® SN
INVADERM® AL
Dye fixing agents

SELLA® FIX E
SELLA® FIX WW
SELLA® FIX WS conc

Levelling and Dispersing Agents
Differences in the size and shape of dye molecules

result in differences in dyeing behaviour
NN NN
Mono-azo (red, yellow)

Cr
NN
NN NN NN
Poly-azo (brown, black) Metal complex

(many colours)

Auxiliary with affinity for the dyes

e.g. INVADERM® LU
- without auxiliary  large difference in dye molecule sizes
Dye A
Dye B
- with auxiliary  more similar dye molecule sizes

LU
Dye A LU Dye B

CIElab co-ordinates for 2 brown dyes

- alone and in combination
50 Brown HH
Brown HC
yellower
HH + HC
40 HH + HC + LU
b*
30
bluer
20
20 30 40 50
greener a* redder

Auxiliary with affinity for the leather

e.g. SELLASOL® TN gran
without auxiliary - different charge density on the leather
- + - + - - + + - - +
with auxiliary - even anionic charge density on the leather
- - - - - - - - - -

Levelling and dispersing agents slow down

the exhaustion of the dye
- hence better dye penetration into the leather
100%
Dye exhaustion
50%
Without auxiliary
With auxiliary
0%
0 10 20 30 40
Time (min)

Guidelines for levelling and dispersing agents
Use INVADERM® LU when different dye types are being mixed
INVADERM® LU is added with the dye
Use SELLASOL® TN gran to disperse and penetrate dyes since

it makes the leather surface more anionic
SELLASOL® TN gran should be added 15 Min. before the dye for

the best effect
Remember: SELLASOL® TN gran does not correct for

differences in dye types

Shade Deepening and Dye Fixing Agents
The use of cationic or amphoteric auxiliaries can influence the

depth of colour and the fixation of the dye
What types are available?
Shade deepening agents

 weak cationic INVADERM® SN
 amphoteric INVADERM® AL
Dye fixation agents

 strong cationic SELLA® FIX E, SELLA® FIX WS conc
 for wet white leathers SELLA® FIX WW

Shade Deepening Agents
INVADERM® SN (weakly cationic, low formaldehyde)
 gives a good increase in shade depth in a safe manner

 easy to apply, best effect at pH 3.2 - 3.5
 safe to use even when residual dyes are in the float
INVADERM® AL (amphoteric, formaldehyde free)
 at high pH values operates as a levelling agent

 at low pH values it is cationic and increases the shade
intensity (shade deepening agent)
Too much shade deepening agent leads to a higher retarding effect
and dye stripping will result  shade weakening effect.

Dye Fixing Agents
SELLA® FIX E (cationic, formaldehyde free)

SELLA® FIX WS conc (cationic, high formaldehyde content)
 very good dye fixing power

 easy to apply in a fresh bath, best effect at pH 3.2 - 3.5
 safe to use when no residual dye is in the float
SELLA® FIX WW (cationic, formaldehyde free)
 very good dye fixing power for wet white leather

 it is used for wet white applications only
Effectiveness of a fixation agent can vary with dye type.

Using cationic fixation agents to exhaust residual dyes in the float
overloads the leather surface and result in poor rub fastness.


FAQ
Are TFL dyes AZO dyes and / or do they contain amines?
Yes, most of our dyes are AZO dyes and they contain amines,
but this has nothing to do with the EU directive, which considers
forbidden amines (carcinogenic substances).
TFL guarantees that all our dyes do not contain any forbidden
amines as stated in the EU directive.
A written TFL statement is available in TFL Internet Website

FAQ
Is the % concentration mentioned in the suffix of a competitor’s

dye, (e.g. 200%) in line with our given % concentration?
No, in most cases the mentioned % concentration is purely

a marketing tool and has nothing to do with spectro strength
value of a dye.
Do our dyes contain free formaldehyde?
In general no, except when a component like formaldehyde

containing dispersing agents are part of the dye.
E.g. light brown or beige dyes.
However, the free formaldehyde amount is not of importance
as the ppm value is in most cases below 100.

FAQ
Why does the light fastness of my customer’s leather

differ form the shade card value?
The light fastness value in the shade card is measured

according to the IUF standard testing method dyed on pure chrome
leather.
The light fastness on customer’s leather is influenced by the

amount of dye used, the penetration, the surface concentration,
amount and characteristic of the cationic and anionic products
used (retanning, fatliquor, etc.).
The light fastness is also influenced by the surface of the article,

as smoother the surface – as lower the light fastness,
as rougher the surface – as higher the light fastness.

FAQ
Why doesn’t TFL provide a list of rub fastness values ?
Some years ago the TFL testing group made a big work on
standard leather and the result was between 4 and 5 for all dyes.
A general list is therefore meaningless.
The rub fastness is strongly influenced by the recipe and

products used.
It is influenced by the fixing of a dye and as more dye you have

concentrated at the surface as lower is the rub fastness.

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Dyes & Dye Auxiliaries

2008, C. Page & F.Wyss 1

Copyright TFL Ledertechnik AG

2008, C. Page & F.Wyss 2

Copyright TFL Ledertechnik AG

Copyright TFL Ledertechnik AG

Our eye can only see light energy

2008, C. Page & F.Wyss 4

Copyright TFL Ledertechnik AG

2008, C. Page & F.Wyss 5

Copyright TFL Ledertechnik AG

In order to evaluate colour,

Under artificial light a colour appears more yellowish

2008, C. Page & F.Wyss 6

Copyright TFL Ledertechnik AG

The colour of an object depends on the

If 2 objects have the same colour under one light

2008, C. Page & F.Wyss 7

Copyright TFL Ledertechnik AG

Colour measurement results of a metameric dyeing

Spectral reflectance graph

2008, C. Page & F.Wyss 8

Copyright TFL Ledertechnik AG

2008, C. Page & F.Wyss 9

Copyright TFL Ledertechnik AG

A coulor is divided into the shade (hue),

shade brightness lightness

2008, C. Page & F.Wyss 10

Copyright TFL Ledertechnik AG

2008, C. Page & F.Wyss 11

Copyright TFL Ledertechnik AG

2008, C. Page & F.Wyss 12

Copyright TFL Ledertechnik AG

CIELab cross section

+ a* values represent red hues

The chroma (C*) is 0 for a purely

The lightness (L*) ranges between

2008, C. Page & F.Wyss 13

Copyright TFL Ledertechnik AG

The spectrophotometer measures the spectral

2008, C. Page & F.Wyss 14

Copyright TFL Ledertechnik AG

Computer colour matching technology helps quickly to respond

• to market trends (fashion)

2008, C. Page & F.Wyss 15

Copyright TFL Ledertechnik AG

Copyright TFL Ledertechnik AG

2008, C. Page & F.Wyss 17

Copyright TFL Ledertechnik AG

Azo dyes are the largest group of synthetic dyes world-wide,

They contain one or more Azo groups as the chromophore

2008, C. Page & F.Wyss 18

Copyright TFL Ledertechnik AG

Monoazo dye: only one Azo group

Dis and polyazo dyes: 2 or more Azo groups

NN NN NN

2008, C. Page & F.Wyss 19

Copyright TFL Ledertechnik AG

Direct Black 168

2008, C. Page & F.Wyss 20

Copyright TFL Ledertechnik AG

NN NN NN

Metal complex dyes are also Azo dyes !