dyestuffs for fashion industry: case study 2 - focus on ... · pdf filedyestuffs for fashion...

Dyestuffs for fashion industry:

Case Study 2 - Focus on contaminations

Bartolini Giuseppe, Franchi Andrea and Dall’Anese Riccardo (BuzziLab – Prato)

July, 18 2017

© - Copyright Laboratorio Buzzi July, 18 2017

May - October 2016: Laboratorio Analisi Buzzi, in collaboration with

CID: first study on contamination levels of dyestuffs.

Chemical Analysis of 4 of the 11 priority groups of Detox MRSL

May - June 2017: second phase of study concerning dyestuffs

previously contaminated on phase one:

Evaluation of contamination within different batches

Evaluation of contamination within different suppliers


Company involved: dyeing mills CID-member :

CROMOS – nobilitazione filati

F.LLI CIAMPOLINI - nobilitazione tessuti

JERSEY-MODE - nobilitazione tessuti

TINTORIA BIAGIOLI MODESTO – tintoria filati

TINTORIA COMETA - nobilitazione filati

TINTORIA FIORDILUCE - nobilitazione filati

FINISSAGGIO T.R.T. - nobilitazione filati

ALESSANDRINI – tintoria filati

BERTO – nobilitazione filati


OPERATIONAL PLAN

1-Data collection among Dyeing mills concerning list of dyestuffs still

in use and confirmation of usage / year

2-Identification of dyestuffs to be analized:

• Screening of most-contaminated dyestuffs (based on previous

study)

• Dyestuffs with same CI was provided by every mills that declared

its usage

3-Chemical analysis: selection of group of substances.


Chemical Analysis: group of «concerned substances»

Parameter MRSL DETOX Limit

Ethoxylated Alkylphenols – APEOS 1 mg/kg

Aromatic amines from azocolorants 1mg/kg

Chlorophenols 0.05 mg/kg

Phthalates 10 mg/kg


ANALYTICAL SECTION

AROMATIC AMINES DERIVED FROM AZO-COLORANTS

Test method compliant to UNI EN ISO 14362-1:2012 Annex F.

Brief description of test method: a weighted sample of dye is treated in

citric buffer with sodium dithionite (reductive cleavage). The released

amine/s is/are extracted in organic solvent and quantitatively analized by

GC-MSMS and LC-MSMS.

Limit of Detection: 0,01mg/kg

Limit of Quantification (MRSL): 1mg/kg


ANALYTICAL SECTION

AROMATIC AMINES from AZO-COLORANTS

LC-MS Agilent 6495 triple quadrupole GC-MS Agilent 7010 triple quadrupole


ANALYTICAL SECTION

APEOS / CHLOROPHENOLS / PHTHALATES

Test Method: in-house method (developed by Buzzi Lab) was used by high-

resolution mass spectrometry/time-of-flight liquid chromatography (LC-QTOF

equipment).

Brief description of test method: a weighted sample of dye is dissolved in organic

solvent and directly analized by LC-QTOF.

This equipment permit the quantitative analysis of APEOS, Chlorophenols and

Phthalates in a single injection, using high-resolution mass spectrometry (exact

masses) with also low-limit of detection.

Limit of Detection: APEOS and Chlorophenols: 0.01mg/kg – Phthalates: 0.1mg/kg

Limit of Quantification (MRSL): APEOS: 1mg/kg – Chlorophenols: 0.05mg/kg –

Phthalates: 10mg/kg


ANALYTICAL SECTION

APEOS / CHLOROPHENOLS / PHTHALATES

LC-Q-TOF

Agilent 6545


RESULTS


Dyestuffs analized

Total: 164 Of which

146 previously analized

(corresponding to 45 C.I.)

and

18 new C.I.


LEVELS of CONTAMINATION

Total dyestuffs: 164

Contamination from APEOS: tot. 177 - 71,3%

Contamination from Aromatic Amines: tot. 111 - 67,8%

Contamination from Chlorophenols: tot. 40 - 24,4%

Contamination from Phthalates: tot. 8 - 4,8%


77

35

26

4 7

7 8

total dyestuffs: 164

acid 77

reactive 35

direct 26

disperse 4

basic 7

pigment 7

leuco 8


APEOS

2

115

APEOS: tot 117

OPEO 2

NPEO 115


APEOS 2

0

1

2

3

1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg 100 - 200 mg/kg > 200 mg/kg

OPEO

57

29 15

5 1

0

10

20

30

40

50

60

1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg 100 - 200 mg/kg > 200 mg/kg

NPEO


AROMATIC AMINES from AZO-COLORANTS

55

14

18

9

4 4

2 1 2

2

Aromatic Amines: tot 111

p-Cl-Aniline 55

4-amino-biphenyl 14

2-naphtylamine 18

p-cresidine 9

o-anisidine 4

2,4-xylidine 4

o-toluidine 2

3,3'-dimethyl-benzidine 1

4-methyl-m-phenylendiamine 2

3,3'-dichloro-benzidine 2


Aromatic

Amines

21 27

6

1

0

5

10

15

20

25

30

1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg

p-chloroaniline

7 8

1 2

0

1

2

3

4

5

6

7

8

9


2-naphtylamine


10

1 2

1

0

2

4

6

8

10

12


4-aminodiphenyl

7

1 1 0 0

1

2

3

4

5

6

7

8


p-cresidine

Aromatic

Amines


0

4

0 0 0

1

2

3

4

5


2,4-xylidine

1

3

0 0 0

1

2

3

4


o-anisidine

Aromatic

Amines


0

2

0 0 0

1

2


4-methyl-m-phenylendiamine

1

0

1

2


3,3'-dimethylbenzidine

Aromatic

Amines


1 1

0 0 0

1

2


3,3'-dichlorobenzidine

2

0 0 0 0

1

2

3


o-toluidine

Aromatic

Amines


CHLOROPHENOLS

28

10

2

Chlorophenols: tot 40

Pentachloro derivatives 28

Tetrachloro derivatives 10

Dichloro derivatives 2


23

5

10

0 2 0

0

5

10

15

20

25

0,05 - 1mg/kg

> 1 mg/kg 0,05 - 1mg/kg

> 1 mg/kg 0,05 - 1mg/kg

> 1 mg/kg

PCP 28 TeCP 3 DiCP 5

Chlorophenols


PHTHALATES

3

1

4

Phthalates: tot 8

DIBP 3

DEHP 1

DINP 4


2

1 1

4

0

1

2

3

4

5

10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg 10 - 50 mg/kg

DIBP DEHP DINP

Phthalates


LEVELS of CONTAMINATION:

COMPARISON between ACTUAL

and PREVIOUS STUDY


APEOS

0

20

40

60

80

100

120

OPEO - 2016 OPEO - 2017 NPEO- 2016 NPEO- 2017

8 (3,5%) 2

(1,3%)

104 (45,6%)

115 (70%)


APEOS

8 (3,5%)

2 (1,2%)

0

1

2

3

4

5

6

7

8

9

10

1 - 10 mg/kg 1 - 10 mg/kg

OPEO - 2016 OPEO - 2017

OPEO


APEOS - NPEO

0

10

20

30

40

50

60

70

1 - 10mg/kg

1 - 10mg/kg

10 - 50mg/kg

10 - 50mg/kg

50 - 100mg/kg

50 - 100mg/kg

100 -200

mg/kg

100 -200

mg/kg

> 200mg/kg

> 200mg/kg

NPEO -2016

NPEO -2017

NPEO -2016

NPEO -2017

NPEO -2016

NPEO -2017

NPEO -2016

NPEO -2017

NPEO -2016

NPEO -2017

61 (27%) 57

(34%)

23 (10%)

29 (17%)

11 (4,8%)

15 (9%)

8 (3%) 5

(3%)

1 1


AROMATIC AMINES from AZO-COLORANT

100

105

110

115

120

125

130

2016 2017

128 (56%)

111 (67%)

Total Contamination



0

2

4

6

8

10

12

14

p-cresidine2016

p-cresidine2017

o-anisidine2016

o-anisidine2017

2,4-xylidine2016

2,4-xylidine2017

14 (6%) 9

(5%)

6 (3%)

4 (2%)

6 (3%)

4 (2%)



0

10

20

30

40

50

60

54 (2%)

55 (3%)

17 (7%) 14

(8%)

15 (6%)

18 (11%)



0

1

2

3

4

5 4 (2%)

2 (1%)

2 (1%)

1 (1%)

1 (1%)

2 (1%)


0

5

10

15

20

25

30

1 - 10mg/kg

1 - 10mg/kg

10 - 50mg/kg

10 - 50mg/kg

50 - 100mg/kg

50 - 100mg/kg

> 100mg/kg

> 100mg/kg

2016 2017 2016 2017 2016 2017 2016 2017

28 (12%)

21 (12%)

21 (9%)

27 (16%)

3 (1%)

6 (3%)

2 (1%)

2 (1%)

4-chloroaniline



0

1

2

3

4

5

6

7

8

1 - 10mg/kg

1 - 10mg/kg

10 - 50mg/kg

10 - 50mg/kg

50 - 100mg/kg

50 - 100mg/kg

> 100mg/kg

> 100mg/kg

2016 2017 2016 2017 2016 2017 2016 2017

6 (2%)

7 (4%)

7 (2%) 8

(4%)

1 (1%)

1 (1%)

2 (1%)

2 (1%)

2-naphtylamine



CHLOROPHENOLS

0

5

10

15

20

25

30

16 (7%)

28 (17%)

3 (2%)

10 (6%)

1 0

5 (2%) 2

(1%) 3

0

Total contaminations


0

5

10

15

20

25

0,05 - 1 mg/kg 0,05 - 1 mg/kg > 1 mg/kg > 1 mg/kg

PCP 2016 PCP 2017 PCP 2016 PCP 2017

12 (5%)

23 (14%)

4 (1,7%)

5 (3%)

Pentachlorophenol - PCP

CHLOROPHENOLS


0

1

2

3

4

5

6

7

8

9

10


TeCP 2016 TeCP2017 TeCP 2016 TeCP 2017

3 (1,3%)

10 (6%)

0 0

Tetrachloro-derivatives

CHLOROPHENOLS


0

1

2

3

4

5


DiCP 2016 DiCP2017 DiCP 2016 DiCP 2017

4 (1,7%)

2 (1,2%)

1

0

Dichloro derivatives

CHLOROPHENOLS


PHTHALATES

0

1

2

3

4

5

DIBP 2016 DIBP 2017 DEHP 2016 DEHP 2017 DINP 2016 DINP 2017

2 (1%)

3 (2%)

1 1

2 (1%)

4 (2%)

Total Contaminations


0

1

2

10 - 50 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg 50 - 100 mg/kg

DIBP 2016 DIBP 2017 DIBP 2016 DIBP 2017

1

2

0

1

PHTHALATES


0

1

2

3

4

5

> 100mg/kg > 100mg/kg 10 - 50 mg/kg 10 - 50 mg/kg

DEHP 2016 DEHP 2017 DINP 2016 DINP 2017

1 1 1

4

PHTHALATES


LEVEL of CONTAMINATION

SINGLES C.I.

(values in mg/kg)

ONLY few EXAMPLES


1,4

0 0 0 0

13,9

7,9

24,2

19

80

0

10

20

30

40

50

60

70

80

90

Supplier A 2016 Supplier A Supplier B Supplier C Supplier D

ACID BLUE 193

chlorophenols

Phthalates

4-chloroaniline

APEOS


0 0 0 0

14,5

45,1

0 0

4,4

4,7

0

6,4

70,4

53,2

5,6

0 0

10

20

30

40

50

60

70

80

Supplier A 2016 Supplier A Supplier B SupplierC

ACID ORANGE 116

chlorophenols

Phthalates

2-naphtylamine

p-cresidine

APEOS


163

60

18 15

4

22

72

81

55

70

4 4

0 0

15

5

0 0

50

100

150

200

Supplier A2016

Supplier A Supplier B Supplier C Supplier D Supplier E Supplier F Supplier G Supplier H

REACTIVE BLACK 5

chlorophenols

Phthalates

4-chloroaniline

APEOS


Complete data of this study

is strictly reserved to CID

members.


CONCLUSIONS

1-total number of contaminations is quite the same respect to 2016;

2-also contamination distributions is quite the same respect to 2016

3-analysis of the same C.I. provided by same mill (so same supplier but

different batch) show that:

In Many cases TOTAL levels of contamination remain unchanged (see

analytical details)

for some Color Index (eg. Reactive Black 5, Acid Red 374) levels of

contamination are lower than previous


CONCLUSIONS

4-analysis of the same C.I provided by different mills (so same C.I. but

different suppliers) show in many cases a different level of

contamination, both in concentration and chemical group

For this reason, is strictly necessary to control the level

of contamination in the next years, in order to start an

action plan for improving the chemical quality of

dyestuffs.


Giuseppe Bartolini [email protected]

Andrea Franchi [email protected]

Riccardo Dall’Anese [email protected]

Buzzi Lab

Laboratorio di Analisi, Prove e

Ricerche Industriali - ITIS T. Buzzi

59100 - PRATO - V.le della

Repubblica,9

Tel + 39 (0)574 - 58.98.87

fax + 39 (0) 574 - 58.98.90

www.buzzilab.it

mailto:[email protected]



http://www.buzzilab/



dyestuffs for fashion industry: case study 2 - focus on ... · pdf filedyestuffs for fashion...

Documents