CN104897665B - The step colour developing examination method of forbidding azo dyes in dyed textiles - Google Patents
The step colour developing examination method of forbidding azo dyes in dyed textiles Download PDFInfo
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- CN104897665B CN104897665B CN201510316854.5A CN201510316854A CN104897665B CN 104897665 B CN104897665 B CN 104897665B CN 201510316854 A CN201510316854 A CN 201510316854A CN 104897665 B CN104897665 B CN 104897665B
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- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000987 azo dye Substances 0.000 title claims abstract description 37
- 239000004753 textile Substances 0.000 title claims abstract description 33
- 239000000523 sample Substances 0.000 claims abstract description 39
- 238000012216 screening Methods 0.000 claims abstract description 22
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000008859 change Effects 0.000 claims abstract description 14
- 239000012488 sample solution Substances 0.000 claims abstract description 13
- 239000012259 ether extract Substances 0.000 claims abstract description 11
- 238000012360 testing method Methods 0.000 claims abstract description 9
- FZRCKLPSHGTOAU-UHFFFAOYSA-N 6-amino-1,4-dimethylcyclohexa-2,4-diene-1-carbaldehyde Chemical compound CC1=CC(N)C(C)(C=O)C=C1 FZRCKLPSHGTOAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 239000007979 citrate buffer Substances 0.000 claims description 4
- 229940079826 hydrogen sulfite Drugs 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000013517 stratification Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 12
- 238000003556 assay Methods 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 description 30
- 150000004982 aromatic amines Chemical class 0.000 description 21
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- 239000004744 fabric Substances 0.000 description 9
- 238000002203 pretreatment Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000000711 cancerogenic effect Effects 0.000 description 3
- 231100000315 carcinogenic Toxicity 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012916 chromogenic reagent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- UCHNVSDXSPIKRG-UHFFFAOYSA-N 1-methoxy-3-(3-methoxyphenyl)benzene Chemical group COC1=CC=CC(C=2C=C(OC)C=CC=2)=C1 UCHNVSDXSPIKRG-UHFFFAOYSA-N 0.000 description 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical class COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 150000005004 2-naphthylamines Chemical class 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- -1 4- aminoazabenzols Amine Chemical class 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical class CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- CXNVOWPRHWWCQR-UHFFFAOYSA-N 4-Chloro-ortho-toluidine Chemical class CC1=CC(Cl)=CC=C1N CXNVOWPRHWWCQR-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical class NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- DSBIJCMXAIKKKI-UHFFFAOYSA-N 5-nitro-o-toluidine Chemical class CC1=CC=C([N+]([O-])=O)C=C1N DSBIJCMXAIKKKI-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004150 EU approved colour Substances 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- BCFQGQUQXZHRDC-UHFFFAOYSA-N N,N-dimethylaniline formaldehyde Chemical compound C=O.CN(C)C1=CC=CC=C1 BCFQGQUQXZHRDC-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of step colour developing examination method of forbidding azo dyes in dyed textiles, comprise the following steps：（1）Sample is reduced；（2）Colour developing：In the same position of filter paper, first it is added dropwise one and drips developer, then 12 drop t-butyl methyl ether extract solution colour developings are added dropwise；The developer is the paradime thylaminobenzaldehyde of mass volume ratio 0.1%~10% and the ethanol solution of the hydrochloric acid of volume ratio 10%~25%；（3）Screening judges：Whether occurs obvious color change after dropwise addition sample solution come judged result according on developer：If obvious color change does not occur after sample solution colour developing, represent that thing to be checked or its concentration are not contained in sample is less than test limit, be as a result feminine gender；If occurring obvious color change after sample solution colour developing, then it represents that forbidding azo dyes may be contained in sample, be as a result the positive, need to be further confirmed that by chromatographic apparatus.Of the invention simple, quick, direct chromogenic assay after sample reduction, whole process color can be completed in 1min.
Description
Technical field
The present invention relates to a kind of step colour developing screening method of forbidding azo dyes in dyed textiles, belong to analytical chemistry
Technical field.
Background technology
From first regulation about Consumer Product Safety in the world：German federal government promulgated on April 10th, 1992
《Food and daily necessities method》The 97/548/EC instructions passed through to European Union in 1997 and the national compulsory mark of China
Quasi- GB 18401-2003《National Textile basic security technical specification》, it is accused of the forbidding azo dyes detection of carcinogenic aromatic amine
Always safety specifications most important, most basic in the trade of International Textile clothes, while being also global consumers in general
Focus of attention during consumption.
Up to the present, the test for forbidding azo dyes in fabric clothing being directed to both at home and abroad has put into effect a series of ripe
Detection method.But there is problems with such method：
（1）Existing detection method is high to the degree of dependence of instrument
At present, the detection method of aromatic amine is disabled in the yarn fabric clothes that European Union, Germany and China all accordingly formulate,
Mainly using the instrument analytical method of the chromatograms such as gas-chromatography, compounds GC-MS, liquid chromatogram or liquid-mass chromatography.Method into
Ripe, accurate, sensitivity is high.But be due to that pretreatment process is complicated, detection process need to be equipped with precision instrument, round of visits compared with
Long, Expenses of laboratory examination is high, and testing conditions are harsh, and the dependence to large-scale chromatographic apparatus is strong, have to the technical merit of practitioner compared with
The reasons such as high request, make this kind of method also be only limitted to the conditional laboratory in part using upper.
（2）The sample size of detection is big
China is the big export country of fabric clothing, and the detection case of forbidding azo dyes is come from textile in recent years
See, substantial amounts of detection demand to detection technique it is efficient, fast propose challenge.
（3）Positive recall rate is low
Weave with China, print and dye, the Environmental Safety consciousness of apparel industry gradually strengthens, and actively researches and develops and use environment-friendly type
Dyestuff, auxiliary agent etc., the quality of exported product and the competitiveness in international market are greatly improved, the harmful substance such as forbidding azo dyes
Recall rate gradually reduce.In recent years, the verification and measurement ratio of actually detected middle textile forbidding azo dyes is less than 1%.
Need not in view of the above-mentioned problems, also establishing some in forbidding azo dyes detection work in fabric clothing at present
Rely on the quick screening method simple, quick, with low cost of large-scale chromatographic apparatus.Detected using the principle rapid screening of colour developing
The method of forbidding azo dyes has been appeared in the newspapers in recent years in textile, such as Chinese patent《One kind is used to disable azo in textile
The rapid screening detection method of dyestuff detection》（The patent No.：200910192737.7）With《Forbidding azo dyes in dyed textiles
Quick determination method》（The patent No.：ZL 201110350255.7）And the article that leaf sunlight cloud tints etc. is delivered in analytical chemistry《It is based on
Forbidding azo dyes fast qualitative screening technique in the textile of diazotising-coupling colour development reaction》.Such method is according to aromatic amine
Architectural feature, introduce diazotising-coupling colour development reaction mechanism, replace traditional chromatographic apparatus to analyze using development process, set up
Forbidding azo dyes quick selective mechanisms method in dyed textiles, important breakthrough is realized in detection technique, is current
Determine forbidding azo dyes detection the most fast and effectively method in textile.
However, the above method still has some defects and deficiency.On the one hand：The sample pre-treatments of method contaminate except azo
Outside the reduction of material, also need to carry out t-butyl methyl ether and the step liquid-liquid extraction of hydrochloric acid two, to realize that fragrant amine extraction and reaction solution decolourize,
Step is still very loaded down with trivial details；On the other hand：Whole process color is the diazonium coupled reaction process of aromatic amine and aldehydes matter, is needed
4 kinds of reagents are used, multistep colour developing, developing time needs about 15min.The method of whole pre-treatment is easy not enough, and colour developing
Method is not quick enough, time-consuming.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide one kind is faster, easier, and the high dyeing of sensitivity is spun
The step colour developing screening method of forbidding azo dyes in fabric.
The reagent of the present invention only includes a kind of developer, is formulated as follows：Mass volume ratio 0.1%-10% to Dimethylaminobenzene
Formaldehyde and volume ratio for 10%~25% hydrochloric acid ethanol solution.
The detection method step of the present invention is as follows：
(1) reduction of sample：Textile samples are with reference to EN 14362-1-2012《Textile is some to come from azo dye
The assay method Part I of the aromatic amine of agent：Determine whether to have used some azo colouring agents through or without extracting fiber
Method》Or the equivalent standard of technology contents carries out reduction pretreatment.Concretely comprise the following steps：Weigh the representative sample that 2.0g is shredded
In reaction bulb, 16mL citrate buffer solutions are added（0.06mol/L, pH=6）With 3.0mL hydrogensulfite solutions
（200mg/mL, matching while using）, reaction bulb is closed, firmly shake, all samples is dipped in liquid, be placed in 70 ± 2 DEG C of water
30min is incubated in bath, is taken out in being cooled to room temperature in 2min.Add 0.5mL NaOH solutions（40% aqueous solution）, 7g sodium chloride,
5mL t-butyl methyl ethers, firmly shake, stratification（If solution milkiness is not stratified, it can centrifuge）, take upper strata t-butyl methyl ether to carry
Take liquid chromogenic assay.
(2) develop the color：In the same position of filter paper, first it is added dropwise one and drips developer, then the t-butyl methyl ethers of 1-2 drops is added dropwise and carries
Liquid is taken to develop the color（Sample extraction solution is dropped on developer）；If the t-butyl methyl ether extract layer of sample has color, in filter paper
Blank position is individually added dropwise 1-2 drop t-butyl methyl ether extract solutions and compareed.
(3) screening judges：Judge knot according to whether occurring obvious color change after the dropwise addition sample solution on developer
Really.
It is negative：Obvious color change does not occur after sample solution colour developing, represents not containing thing to be checked or its concentration in sample
Less than test limit.
It is positive：Occur obvious color change after sample solution colour developing, then it represents that forbidding azo dyes may be contained in sample,
It need to be further confirmed that by chromatographic apparatus.
Wherein, described filter paper is slow filter paper.
The formula of the developer paradime thylaminobenzaldehyde and volume ratio that preferably mass volume ratio is 1% are 25%
The ethanol solution of hydrochloric acid.
Advantages of the present invention：The present invention uses filter paper development process rapid screening aromatic amine, simple, quick, after sample reduction
Direct chromogenic assay, without liquid-liquid extraction, without concentration, without decolourizing；Without any instrument and equipment in measure, using only one kind
Developer, is added dropwise colour developing on filter paper, and naked eyes are seen and looked into, and whole process color can be completed in 1min.For current weaving
The product forbidding azo dyes detection present situation that sample size is big, positive rate is low, the screening method is quick, accurate, low cost, really
Realize the rapid screening of textile forbidding azo dyes.Because without equipment investment, cost is low, and technology is simple, it is easy to grasp,
The quick screening for being allowed to can be not only used for textile inspection mechanism can be used for the Self-control of manufacturing enterprise again, have a wide range of applications
Prospect.
Brief description of the drawings
Forbidding azo dyes operational flowchart in the existing determination of color dyed textiles of Fig. 1.
The operational flowchart of Fig. 2 the inventive method.
Embodiment
Further illustrate the present invention below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1-29：The testing result of 29 actual cloth samples
First, develop the color agent prescription：By 1g N, N- dimethyl -4- aminobenzaldehydes add after the dissolving of 75mL ethanol, add 25mL
Used after hydrochloric acid, mixing.
Secondly, naphthylamines containing 2-, parachloroanilinum, ortho-aminotoluene, 3,3 '-dimethoxy-biphenyl are detected to the instrument being collected into
8 kinds of disabling fragrance such as amine, 5- nitro-o-toluidines, 2,4 di amino toluene, 2,4- diamino anisoles and 4- aminoazabenzols
Amine, content range is measured from 5 mg/kg -557 mg/kg 29 cloth samples according to the step of the present invention, is shown
Color, this method recall rate 100%, no false negative.Comprise the following steps that：
（1）The reduction of sample：Representative sample that 2.0g shreds is weighed in reaction bulb, 16mL citrates is added and delays
Rush solution（0.06mol/L, pH=6）With 3.0mL hydrogensulfite solutions（200mg/mL, matching while using）, reaction bulb is close
Close, firmly shake, all samples is dipped in liquid, be placed in 70 ± 2 DEG C of water-baths and be incubated 30min, take out in cooling in 2min
To room temperature.Add 0.5mL NaOH solutions（40% aqueous solution）, 7g sodium chloride, 5mL t-butyl methyl ethers firmly shake, stratification
（If solution milkiness is not stratified, it can centrifuge）, take upper strata t-butyl methyl ether extract solution chromogenic assay.
（2）Colour developing：In the same position of slow filter paper, first it is added dropwise one and drips developer, then the t-butyl methyl ether of 1-2 drops is added dropwise
Extract solution develops the color（Sample extraction solution is dropped on developer）；If the t-butyl methyl ether extract layer of sample has color, in filter paper
Blank position 1-2 drop t-butyl methyl ether extract solutions be individually added dropwise compare.
（3）Screening judges：Judge knot according to whether occurring obvious color change after the dropwise addition sample solution on developer
Really.
It is negative：Obvious color change does not occur after sample solution colour developing, represents not containing thing to be checked or its concentration in sample
Less than test limit.
It is positive：Occur obvious color change after sample solution colour developing, then it represents that forbidding azo dyes may be contained in sample,
It need to be further confirmed that by chromatographic apparatus.
The specific screening results of 29 actual cloth samples are as shown in table 1.
The inventive method of table 1 is to actual sample screening results
The detection limit of the inventive method：
For the detection limit of verification method, certain density aromatic amine standard liquid is added into citrate buffer solution and company
Chromogenic assay after sodium sulfite solution reduction.After colour developing, more obvious color change can be visually observed for foundation, is sentenced
The method detection limit of the fixed aromatic amine.
Concretely comprise the following steps：24 kinds of carcinogenic aromatic amines of 1mL 15mg/L and 1mL 30mg/L are pipetted respectively and aniline standard is molten
Liquid adds 16mL citrate buffer solutions and 3.0mL hydrogensulfite solutions, and reaction bulb is closed, firmly shakes, is placed in
30min is incubated in 70 ± 2 DEG C of water-baths, is taken out in being cooled to room temperature in 2min.Add 0.5mL NaOH solutions, 7g sodium chloride, 5mL
T-butyl methyl ether, firmly shakes, stratification（If solution milkiness is not stratified, it can centrifuge）.
Using slow filter paper, the same position in filter paper is selected, one is first added dropwise and drips developer, then the 1-2 drop tert-butyl groups are added dropwise
Methyl ether extract solution, colour developing.
Method is to the detection limit of 24 kinds of carcinogenic aromatic amines and aniline up to 7.5mg/kg-15mg/kg.At present, European Union includes
Germany is 24 about the disabling aromatic amine of rules and regulations, and it is 30mg/kg that maximum limitation is detected on the textile；Oeko-Tex
It is 24 that standard 100 and the regulations of China GB 18401, which disable aromatic amine, and it is 20mg/kg that maximum limitation is detected on the textile.
The detection limit of this method is less than Limited Doses as defined in domestic and international laws and regulations at present.
Compared with existing testing methods of banned azo dyes in textiles, advantages of the present invention：
The detection of forbidding azo dyes is generally divided into two big steps in textile.1st step is sample pre-treatments, and azo is contaminated
Material is reduced to aromatic amine, and is purified, concentrated.2nd step is to determine, and determines the fragrant amine content extracted.Determined with existing
Method is compared, and the technology of the present invention enormously simplify two big steps, realize in dyed textiles forbidding azo dyes it is quick
Screening.
（1）Contrasted with existing Instrument measuring method
Forbidding azo dyes examination criteria in existing relevant textile, uses the method that instrument is detected both at home and abroad.
1st step sample pre-treatments typically using reduction, cross post separation, concentration, the means such as constant volume, the 2nd pacing surely using gas chromatograph,
The separation of the large-scale precision instrument such as gas chromatograph-mass spectrometer (GC-MS) or liquid chromatograph, measure aromatic amine.Such method is accurate, can
Lean on, but complex pretreatment, it is necessary to be equipped with precision instrument, round of visits is longer, Expenses of laboratory examination is high, and professional technique people need to be equipped with
The testing agency of member completes, and condition is harsh.The technology of the present invention only need on filter paper chromogenic assay, by naked eyes offer an explanation, without appoint
What large-scale chromatographic apparatus equipment；Pre-treatment step only needs one step of reduction, without concentration, purification；Whole experimental implementation is simple, reagent
Consumption is few, cost is low, the time is fast, and general enterprise laboratory is also independently operable.In reagent cost, instrument cost, experiment consumption
When in terms of specific compare as shown in table 2- tables 4.Reagent cost needed for this method is the 3% of existing instrument detection method；Required instrument
Device cost is the 0.6% of existing detection method；It is only the 25% of existing detection method the time required to 1 sample of detection.
The reagent cost of table 2 is contrasted
The instrument cost of table 3 is contrasted
The time-consuming contrast of the experiment of table 4
（2）Contrasted with existing quick screening method
Pertinent literature is consulted, the method for detecting forbidding azo dyes in textile using the principle rapid screening of colour developing has
Report, such as patent《It is a kind of to be used for the rapid screening detection method that forbidding azo dyes are detected in textile》（The patent No.：
200910192737.7）；Patent《Forbidding azo dyes quick determination method in dyed textiles》（The patent No.：ZL
201110350255.7）.Such method introduces diazotising-coupling colour development reaction mechanism according to the architectural feature of aromatic amine, with aobvious
Color method replaces traditional chromatographic apparatus to analyze, and establishes the quick selective mechanisms method of forbidding azo dyes in dyed textiles,
Important breakthrough is realized in dyed textiles forbidding azo dyes detection technique, is forbidding azo dyes in current measure textile
Detection the most fast and effectively method.
However, in terms of sample pre-treatments：The sample pre-treatments of such method needed in addition to the reduction of azo dyes, also into
Row t-butyl methyl ether and the step liquid-liquid extraction of hydrochloric acid two, to realize that fragrant amine extraction and reaction solution decolourize；After the reduction of this method sample
Chromogenic assay can be directly carried out, without other pre-treatment steps.In process color：Existing patent and literature method, colour developing are needed
4 kinds of reagents are used, multistep colour developing, developing time needs about 15min.Present invention colour developing only needs a kind of developer, then filter paper previous step
Colour developing, whole developing time can be completed in 1min.As shown in Figure 1 and Figure 2.
Integrated comparative, method of the invention is all significantly better than existing instrument in sample pre-treatments and process color
And chromogenic assay method.Simple to operate, reagent dosage is few, speed is fast, cost is low.
Compared with similar development process, significant difference of the invention：
Although existing document report uses paradime thylaminobenzaldehyde for developer, colorimetric estimation urea, hydrazine, indoles,
Tryptophan, hydrazine etc., but the present invention is by comparison, with significant difference and more excellent effect.
1. filter paper color developing effect is substantially better than colorimetric cylinder colour developing
Have been reported the document that object is determined by developer of paradime thylaminobenzaldehyde, the colorimetric used without exception
Pipe colorimetric, the method for spectrophotometric determination.For contrast filter paper colour developing with colorimetric cylinder colour developing it is dramatically different, experiment is respectively adopted
Filter paper and plastic centrifuge tube develop the color, and the step of wherein filter paper develops the color is：Using slow filter paper, the same position in filter paper is selected,
First it is added dropwise one and drips developer, then 2 drop 30mg/L aromatic amine standard liquid is added dropwise, observes color developing effect（The inventive method）.From
Heart pipe development step is：First it is added dropwise one and drips developer, then 2 drop 30mg/L aromatic amine standard liquid is added dropwise, mixes.
Experimental Comparison 12 aromatic amines two kinds of color developing effects：With the sensitive 4- aminobphenyls of chromogenic reagent, benzidine,
Two kinds of the aromatic amine of 2- naphthylamines, 4- chloroanilines etc. 7 colour developing mode naked eyes can distinguish its color change, and it is less sensitive to develop the color
4- chloro-o-toluidines, 3,3 '-dimethoxy benzidine, 3,5 aromatic amines such as 3 '-dimethylbenzidine, filter paper development process can
Obvious chromosphere generation is observed visually, and centrifuge tube color developing effect is difficult to differentiate between with blank, it is impossible to differentiate.The effect of filter paper colour developing
Fruit is substantially better than the colour developing in centrifuge tube.
Developed the color in centrifuge tube, in organic solvent, concentration is reduced for the coloring matter dissolving that developer is generated with object,
What is shown is of light color, can not visually be distinguished after causing the weak aromatic amine colour developing of developing portions；Filter paper development process, organic solvent volatilization
Afterwards, the coloring matter of generation is only remained, certain inspissation is served, color depth is deep.Meanwhile, chromogenic reagent solution is in itself in Huang
Color, thus blank solution（The 1 drop drop t-butyl methyl ether of developer+2）, also it is presented certain light yellow in centrifuge tube, but drop in
Then it is shown as on filter paper colourless.It can be seen that, the color of blank can effectively be removed using filter paper method colour developing, while beneficial to organic solvent
Volatilization play certain inspissation, be easy to the discrimination of color to compare.This just makes traditional colorimetric cylinder colorimetric method not distinguish
Color, it is clearly discernible using filter paper development process, realize the colour developing screening of 25 kinds of amine substances.
2. filter paper colour reagent consumption is few
In the detection pretreatment process of textile forbidding azo dyes, using the extraction of 5mL t-butyl methyl ethers after sample reduction,
Yet with reasons such as miscible and cloth the absorptions with aqueous phase, the t-butyl methyl ether used only 2- can be extracted after extraction
3mL, according to spectrophotometry, only cuvette just at least needs 4mL solution, according to sample and developer 2:1 body
Product ratio, sample size is inadequate；The present invention only needs 1-2 drop sample solutions, and sample volume consumption is few, and remaining sample can provide the later stage simultaneously
GC-MS qualitative, quantitatives confirmation is used.
3. it is simple and efficient
, it is necessary to use spectrophotometer during spectrophotometry, the instrument and equipment such as colorimetric cylinder, and a colorimetric
Pipe is simply possible to use in the colorimetric of a sample；This law only needs filter paper, and dropper is distinguished with naked eyes, moreover, a filter paper can be simultaneously
The colour developing screening of multiple samples is carried out, simple and efficient, reagent consumables cost is substantially reduced.
Claims (4)
1. the step colour developing examination method of forbidding azo dyes in a kind of dyed textiles, it is characterised in that comprise the following steps：
（1）Sample is reduced：Representative sample that 2.0g shreds is weighed in reaction bulb, 16mL0.06mol/L is added, pH=6
The hydrogensulfite solution that citrate buffer solution and 3.0mL200mg/mL now match somebody with somebody, reaction bulb is closed, firmly shake,
All samples is dipped in liquid, be placed in 70 ± 2 DEG C of water-baths and be incubated 30min, take out in being cooled to room temperature in 2min；Add
0.5mL concentration is the 40% NaOH aqueous solution, and 7g sodium chloride, 5mL t-butyl methyl ethers firmly shake, stratification, take upper strata uncle
Butyl methyl ether extract solution；
（2）Colour developing：In the same position of filter paper, be first added dropwise one and drip developer, then be added dropwise 1-2 drops t-butyl methyl ether extract solution it is aobvious
Color；The developer is the ethanol solution of paradime thylaminobenzaldehyde and hydrochloric acid, the paradime thylaminobenzaldehyde to hydrochloric acid and
The mass volume ratio of ethanol is 0.1%~10%, and the volumes of aqueous ethanol ratio of the hydrochloric acid is 10%~25%；
（3）Screening judges：Whether occurs obvious color change after dropwise addition sample solution come judged result according on developer：If
Obvious color change does not occur after sample solution colour developing, represents that thing to be checked or its concentration are not contained in sample is less than test limit, knot
Fruit is feminine gender；If occurring obvious color change after sample solution colour developing, then it represents that forbidding azo dyes may be contained in sample, tie
Fruit is the positive, need to be further confirmed that by chromatographic apparatus.
The examination method 2. a step according to claim 1 develops the color, it is characterised in that described filter paper is slow filter paper.
The examination method 3. a step according to claim 1 develops the color, it is characterised in that the formula of the developer is preferably to two
Methylamino phenenyl formaldehyde is 1% to the mass volume ratio of hydrochloric acid and ethanol, and the volumes of aqueous ethanol ratio of the hydrochloric acid is 25%.
The examination method 4. a step according to claim 1 develops the color, it is characterised in that when the t-butyl methyl ether extract layer of sample has
Color, 1-2 drop t-butyl methyl ether extract solutions need to individually be added dropwise in the blank position of filter paper and compare.
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| CN108459018B (en) * | 2018-06-25 | 2023-11-28 | 中联品检(福建)检测服务有限公司 | Textile formaldehyde detection device and detection method |
| CN109541080A (en) * | 2019-01-16 | 2019-03-29 | 深圳天祥质量技术服务有限公司 | The detection method of azo dyes in water |
| CN110455952A (en) * | 2019-08-21 | 2019-11-15 | 珠海天祥粤澳质量技术服务有限公司 | Azo and aromatic amine compounds quick screening method in a kind of food |
| CN110793949A (en) * | 2019-11-12 | 2020-02-14 | 杭州百合科莱恩颜料有限公司 | Method for rapidly and semi-quantitatively determining concentration of residual aromatic amine in aromatic amine diazonium salt |
| CN111721881A (en) * | 2020-07-07 | 2020-09-29 | 东莞诺威检测认证有限公司 | A detection method for banned azo dyes in textiles using trifluoroacetylated gas chromatography-mass spectrometry |
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| CN101671945B (en) * | 2009-09-27 | 2010-12-01 | 广东出入境检验检疫局检验检疫技术中心 | Rapid screen detection method used for banned azo dyes detection in textiles |
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