The first synthetic dye was invented by William Perkin in the middle of the 19th Century and, for a long time, there was no awareness of, or concern for, the harmful effects that a lot of these dyes had on Man and on the environment.

With the advent of environmental concerns in developed countries, particulary in Europe, research led to specific conclusions regarding the damaging effects associated with the use of certain products in consumption goods.

Germany stands out in this field, having developed very clear standards which limit the use and manufacture of textiles which include products or substances which were identified as dangerous.

Due to these initiatives, the Textile Industry, which uses over 500 dyes and products in related categories, can today be considered a less-polluting industry.

The standards are extremely clear and restrictive and manufacturers today have very specific criteria on these issues to ensure that goods will be accepted in the various international markets, which themselves are extremely strict in following what is stipulated by the “ECO” standards.

These standards vary according to the country and the end purpose of the goods (baby, adult, work clothes, etc.) and restrict the use of the following chemicals:

Azoic dyes which contain forbidden amides;

• Chlorinated phenols;
• Formaldehyde;
• Extractable heavy metals;
• Residual pesticides;
• Allergenic dyes;
• Chlorinated benzenes and toluene compounds;
• Phthalates;

It was therefore important to find a way to certify, and highlight, manufacturers that were meeting these standards, in a way that ensured that consumers were also aware.

Thus the following labels were born:

“ECO” the “Friends of the Environment”

These labels can be divided into 2 categories:

Those which are granted by government bodies (I) and those which are granted by private bodies (II).

Some examples:

(I)

• Eco Mark (Japan)
• Flower (EEC)
• Green Seal (USA)

(II)

• OekoTex 100 ( Germany / Austria)
• GuT - carpetes ( Germany)
• Tox Proof - TUV (Germany)

In the Federal Republic of Germany, the following legal regulations related to ecology in textiles are currently in place:

• Law for Food and Consumption Goods – Covers disperse allergenic dyes and chromium VI.
• Regulations for consumption goods – Flame retardants, azoic dyes, nickel and formaldehyde.
• Regulations for forbidden chemicals – DDT, Dioxins and Furans, mercury, PCB, PCT, PCP, Flame Retardants and Azoic Dyes.

A) Criteria for the design of the ECO labels

• Group I – Baby clothing
• Group II – Materials in contact with the skin
• Group III – Materials which are not in contact with the skin

B) Processes

There are recommendations to avoid certain processes, such as bleaching using hypochlorite and dyeing polyester using carriers based on organic chlorine compounds.

C) Colour fastness properties

When applied to the respective fibres, only 50 to 90% of the total dye is fixed. The remainder is either released in effluents or stays on the surface of the fibre and is transferred onto skin when it comes into contact with it. Therefore, the colour fastness properties, during washing and friction, are also part of the requirements for the design of the “ECO” labels.

D) ECO Limits

The tables included below display the limits for certain substances in finished textile materials.

ECO ACCEPTED LIMITS

01 – Presence of forbidden amides	< 30 ppm
02 – Presence of Pentachlorophenol (PCP)	< 0.5 ppm (< 0.05 ppm for baby clothing)
03 – Presence of formaldehyde	< 300 ppm (materials not in contact with the skin)< 75 ppm (materials in contact with the skin)<20 ppm (baby clothing)
04 – Presence of heavy metals (OecoTex)	See table below
05 – Residual pesticides	< 1ppm (0.5ppm for baby clothing)
06 – Allergenic dyes	Listed
07 – Carcinogenic dyes	Listed
08 – Chlorinated benzenes and toluene	< 1 ppm
09 – Presence of phthalates	< 0.01 ppm
10 – Organic compounds which include tin (TBT, DBT - tributyltin, dibutyltin)	< 1 ppm (0,5 ppm for baby clothing)
11 – Ph level of the aqueous solution	Ph 4.5 - 7.5
12 – Colour fastness Rating	See tabl

Additional notes on some of the parameters mentioned above:

01 – Some of the roughly 2 000 Azoic dyes on the market are banned given that they can produce, by reduction – chemical or microbiological – carcinogenic arylamines, and these are mainly Acid, Basic, Direct and Disperse.

The acceptable amide limit in textiles is 30mg/Kg or 30 ppm and, while not legally regulated, the limit for the same amides in dyes is 150 mg/Kg or 150 ppm.

04 – The limits given below are measured in mg/Kg or ppm:

Heavy Metal	Baby clothing	Clothes in contact with skin	External clothing
Antimony	30	background-color: transparent”> 30	30
Arsenic	0.20	background-color: transparent”> 1	1
Cadmium	0.10	background-color: transparent”> 0.10	0.10
Chromium	1	background-color: transparent”> 2	2
Chromium VI	undetectable	undetectable	<0.05
background-color: transparent”> Cobalt	1	4	4
Copper	background-color: transparent”> 25	50	50
Lead	background-color: transparent”> 0.2	1	1
Nickel	1	4	4
Mercury	0.02	0.02	0.02

IMPORTANT NOTE: The values given above refer to heavy metals which can be extracted through saliva and/or perspiration and which can be transferred onto the skin under certain usage conditions. They should therefore not be confused with the total level of heavy metals contained in the textile material.

06 – It is known that certain disperse dyes can cause allergic reactions in humans.

Polyamide and cellulose acetate, when dyed using the disperse dyes considered, show poor colour fastness in damp environments, which results in a transfer of the dye onto the skin. The most common textile articles in this context are women’s socks and stockings. On the other hand, the use of these same dyes on 100% Polyester fibres results in excellent colour fastness!

List 1) – Dyes deemed to be allergenic according to German Legislation:

• Disperse Yellow 1 / 3
• Disperse Orange 3 / 37 / 76
• Disperse Red 1
• Disperse Blue 1 / 35 / 106 / 124

List 2) - Dyes deemed to be allergenic according to OekoTex 100

• Disperse Yellow 1 / 9 / 39 / 49
• Disperse Orange 1
• Disperse Red 1 / 17
• Disperse Blue 3 / 7 / 26 / 106
• Disperse Brown 1

07 – Carcinogenic dyes

• Acid Red 26
• Basic Red 9
• Basic Violet 14
• Direct Black 38
• Direct Red 28
• Direct Blue 6
• Disperse Yellow 3
• Disperse Orange 11
• Disperse Blue 1

12 – Colour Fastness Ratings
The OekoTex 100 norms recommend that finished textile materials should have the following colour fastness ratings:

Solidity	Baby clothing	Clothing in contact with skin	Clothing not in contact with skin
Water	3	3	3
Acid perspiration	3-4	3-4	3-4
Alkaline perspiration	3-4	3-4	3-4
Dry friction	4	4	4
Saliva	5

Final note

German legislation stipulates standards for dyed, printed and finished materials and the quality of these textiles depends on other variables besides the dyes used, namely the substrate, the preparation, dyeing, printing and finishing conditions, as well as the chemicals and auxiliary products used.