dyestuffs for fashion industry: case study 2 - focus on ... · pdf filedyestuffs for fashion...
TRANSCRIPT
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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.
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
ANALYTICAL SECTION
AROMATIC AMINES from AZO-COLORANTS
LC-MS Agilent 6495 triple quadrupole GC-MS Agilent 7010 triple quadrupole
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
ANALYTICAL SECTION
APEOS / CHLOROPHENOLS / PHTHALATES
LC-Q-TOF
Agilent 6545
© - Copyright Laboratorio Buzzi July, 18 2017
RESULTS
© - Copyright Laboratorio Buzzi July, 18 2017
Dyestuffs analized
Total: 164 Of which
146 previously analized
(corresponding to 45 C.I.)
and
18 new C.I.
© - Copyright Laboratorio Buzzi July, 18 2017
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%
© - Copyright Laboratorio Buzzi July, 18 2017
77
35
26
4 7
7 8
total dyestuffs: 164
acid 77
reactive 35
direct 26
disperse 4
basic 7
pigment 7
leuco 8
© - Copyright Laboratorio Buzzi July, 18 2017
APEOS
2
115
APEOS: tot 117
OPEO 2
NPEO 115
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
2-naphtylamine
© - Copyright Laboratorio Buzzi July, 18 2017
10
1 2
1
0
2
4
6
8
10
12
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
4-aminodiphenyl
7
1 1 0 0
1
2
3
4
5
6
7
8
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
p-cresidine
Aromatic
Amines
© - Copyright Laboratorio Buzzi July, 18 2017
0
4
0 0 0
1
2
3
4
5
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
2,4-xylidine
1
3
0 0 0
1
2
3
4
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
o-anisidine
Aromatic
Amines
© - Copyright Laboratorio Buzzi July, 18 2017
0
2
0 0 0
1
2
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
4-methyl-m-phenylendiamine
1
0
1
2
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
3,3'-dimethylbenzidine
Aromatic
Amines
© - Copyright Laboratorio Buzzi July, 18 2017
1 1
0 0 0
1
2
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
3,3'-dichlorobenzidine
2
0 0 0 0
1
2
3
1 - 10 mg/kg 10 - 50 mg/kg 50 - 100 mg/kg > 100 mg/kg
o-toluidine
Aromatic
Amines
© - Copyright Laboratorio Buzzi July, 18 2017
CHLOROPHENOLS
28
10
2
Chlorophenols: tot 40
Pentachloro derivatives 28
Tetrachloro derivatives 10
Dichloro derivatives 2
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
PHTHALATES
3
1
4
Phthalates: tot 8
DIBP 3
DEHP 1
DINP 4
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
LEVELS of CONTAMINATION:
COMPARISON between ACTUAL
and PREVIOUS STUDY
© - Copyright Laboratorio Buzzi July, 18 2017
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%)
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
AROMATIC AMINES from AZO-COLORANT
100
105
110
115
120
125
130
2016 2017
128 (56%)
111 (67%)
Total Contamination
© - Copyright Laboratorio Buzzi July, 18 2017
AROMATIC AMINES from AZO-COLORANT
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%)
© - Copyright Laboratorio Buzzi July, 18 2017
AROMATIC AMINES from AZO-COLORANT
0
10
20
30
40
50
60
54 (2%)
55 (3%)
17 (7%) 14
(8%)
15 (6%)
18 (11%)
© - Copyright Laboratorio Buzzi July, 18 2017
AROMATIC AMINES from AZO-COLORANT
0
1
2
3
4
5 4 (2%)
2 (1%)
2 (1%)
1 (1%)
1 (1%)
2 (1%)
© - Copyright Laboratorio Buzzi July, 18 2017
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
AROMATIC AMINES from AZO-COLORANT
© - Copyright Laboratorio Buzzi July, 18 2017
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
AROMATIC AMINES from AZO-COLORANT
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
0
1
2
3
4
5
6
7
8
9
10
0,05 - 1 mg/kg 0,05 - 1 mg/kg > 1 mg/kg > 1 mg/kg
TeCP 2016 TeCP2017 TeCP 2016 TeCP 2017
3 (1,3%)
10 (6%)
0 0
Tetrachloro-derivatives
CHLOROPHENOLS
© - Copyright Laboratorio Buzzi July, 18 2017
0
1
2
3
4
5
0,05 - 1 mg/kg 0,05 - 1 mg/kg > 1 mg/kg > 1 mg/kg
DiCP 2016 DiCP2017 DiCP 2016 DiCP 2017
4 (1,7%)
2 (1,2%)
1
0
Dichloro derivatives
CHLOROPHENOLS
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
LEVEL of CONTAMINATION
SINGLES C.I.
(values in mg/kg)
ONLY few EXAMPLES
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
Complete data of this study
is strictly reserved to CID
members.
© - Copyright Laboratorio Buzzi July, 18 2017
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
© - Copyright Laboratorio Buzzi July, 18 2017
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.
© - Copyright Laboratorio Buzzi July, 18 2017
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