CN106959344A - The assay method of sensitization fragrance level and volatile quantity in a kind of textile material - Google Patents
The assay method of sensitization fragrance level and volatile quantity in a kind of textile material Download PDFInfo
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Abstract
The present invention relates to a kind of assay method for being related to sensitization fragrance level and volatile quantity in a kind of textile material especially textile toy, described assay comprises the following steps：(1) sample pre-treatments：Textile sample is through acetone ultrasonic extraction, and supernatant liquor crosses the organic filter membrane of micropore；(2) in GC MS determination samples 48 kinds of sensitization aromatic content.Described volatile quantity is determined as sensitization aromatic volatile quantity in the method detection textile material sample using Head space gas chromatography combined with mass spectrometry (HS GC MS).Described textile material sample includes but is not limited to routine use using pure cotton material, polyester material, cotton ramie blended spinning material as the textile material product of raw material, preferably textile toy.
Description
Technical field
The invention belongs to technical field of biological, played in particular to a kind of textile material especially textile
The assay method of sensitization fragrance level and volatile quantity in tool.
Background technology
Aromatic is most common allergenic substance.When skin contacts these materials, allergy can be produced and become skin
Red, oedema, or even produce inflammation.Allergic reaction can not be cured, and can only treat these symptoms.2% children couple are there are about in Europe
Aromatic allergy.Only avoid skin from contacting allergenic substance, Contact hyper sensitization could be prevented.But aromatic in toy etc. very
Used on multi-product, many children can not avoid contacting with these materials, so the use of aromatic should be controlled strictly.
European Parliament is formally instructed by 2009/48/EC toy safeties, proposes to forbid first in toy using 55 kinds of allergy
Property aromatic (content be no more than 100mg/kg), and 11 kinds of anaphylaxis fragrance levels when surpassing 0.01% needs be identified.
Also clearly propose that the chemical composition in toy material must be with European Union on dangerous material material classification, packaging and label regulation phase one
Cause.In April, 2012, European Union harmonized stndard EN71-13《Safety of toys-Part 13:Olfactory board
games,gustative board games,cosmetic kits and gustative kits》Fragrance is further refined
The requirement of agent, 66 kinds of original restricted substances are reclassified, and be divided into 40 kinds of disabling flavouring agents and 26 kinds limit the use of flavouring agent, but
It is that the total and specific material of restricted substances does not change.
It is that the life of children brings the happy of many, but also give simultaneously with the development advanced by leaps and bounds of toy industry
Children itself bring new potential hazard.Outlet of the toy safety new command that European Union puts into effect to Chinese toy product is proposed
Harsh requirement, influence is produced for Chinese toy Export Industry.But European Union does not issue the side that aromatic is determined in toy
Method standard, the national standard of China is to inspection and quarantine professional standard also without related examination criteria.For reply anaphylaxis aromatic
Instruction, this research intends based on the advanced technology such as head space and gas chromatography mass spectrometry, sets up complete, accurately and rapidly disabling sensitization fragrance
Agent and the detection method for limiting the use of aromatic, effectively can be monitored, and can be China to importing and exporting harmful substance in toy
The use of aromatic provides reliable risk assessment data in toy.
Now, have more than 5000 kinds of distinct fragrance agent makes in cosmetics, household articles, textile, footwear and toy
With.European Union does not issue the standard method that aromatic is determined in toy, the national standard and inspection and quarantine professional standard of China
Without related examination criteria.In addition, in order to more preferably carry out reliable risk assessment to sensitization aromatic in the consumer goods, monitoring children
To the exposure suction level of sensitization aromatic, it is necessary to know release conditions of the sensitization aromatic into environment.It is domestic at present to be somebody's turn to do
Aspect work is not yet carried out, and foreign countries are had been reported that using Headspace-solid phase microextraction-gas chromatography mass spectrometry method (Solid-Phase
Microextraction and Gas Chromatography-Mass Spectrometry), such as Gerd Knupp et al. are used
This method identifies 12 kinds of aroma ingredients in perfume, and F.Bothe et al. determines the family expenses such as scented candle, liquid detergent, clothing softening agent
Sesame oil composition in product, Yong Chen et al. determine the aromatic compound in shampoo, Marcel ZHU researchs with SPME methods
The volatilization process of 17 kinds of aroma ingredients in perfumed soap, the research such as J.Pablo Lamas shows, solid with head space in the baby bathing water
Phase extraction technology is capable of detecting when sensitization aromatic.
At present both at home and abroad in few toys sensitization aromatic correlative study, the report in 2010 such as Ines Masuck
Using Headspace-solid phase microextraction-gas chromatography mass spectrometry method to grinding that sensitization aromatic burst size in plastic toy 24 is measured
Study carefully, as a result show, burst size number have direct pass with the content of contained sensitization aromatic in the environment temperature and toy of release
System, operation temperature is higher, fragrance level is higher, and burst size is also bigger.Ines Masuck et al. report is not directed to Europe
The all substances that alliance toy instruction 2009/48/EC is included, and the toy sample analyzed, only PVC plastic material are a kind of,
Fail to cover all materials of the fragrant toys of market sale.Mechanism is mainly CIQ to studies in China earlier
Research institute and Shanghai Entry-Exit Inspection and Quarantine bureau, its mainly study including：Skill is used in conjunction using thermal desorption-gas chromatography mass spectrum
38 kinds of sensitization aromatic in art detection cotton flannel toy, 21 kinds of virtues in measure toy are used in conjunction using gas phase chromatogram-ion trap mass spectrum
Pastil, 5 kinds of cumarins etc., its detection compound quantity and species and Europe are detected in toy using efficient liquid phase-tandem mass spectrometry
The requirement of alliance also has gap, secondly, and detection matrix is not complete, and method extracts complex, furthermore, the instrument used is not very general
And, therefore necessary a kind of simple, quick, high flux is set up according to unlike material, detecting instrument is used in each laboratory
The detection method of popularization.
Inventor instructs involved sensitization aromatic assay method to carry out comprehensive research 2009/48/EC, to difference
The research of sensitization aromatic extraction and cleaning condition in the fragrant toys of material, and sensitization aromatic burst size in toy is ground
Study carefully, urgently carry out in China's toy inspection industry, set up complete, accurately and rapidly sensitization aromatic detection method, can
It is effective to be monitored to importing and exporting harmful substance in toy, and reliable wind can be provided for the use of aromatic in China's toy
Assess data in danger.In addition, inventor also expands the research that aromatic is detected in scent pens first.Scent pens are deep by vast medium and small
What student was even grown up likes, and does not have any correlative study both at home and abroad at present, and the aromatic problem in scent pens does not cause
It is social to pay attention to extensively.Research finds there is sensitization flavouring agent in scent pens, there is risk to health.
The present invention have studied 53 kinds of chemical constitutions and the big sensitization aromatic of nature difference, and very many in quantity,
The sensitization flavouring agent standard items resulted in the world at present are covered, screening and the confirmation side of a kind of many compounds is established
Method, is mainly used in for the aromatic detection in plastics, the toy of textile material matrix and scent pens.
The content of the invention
Present invention firstly relates in a kind of method of gas chromatography-mass spectrography (GC-MS) detection textile material sample
The method of sensitization fragrance level.
The invention further relates to a kind of method of Head space-gas chromatography-mass spectrography (HS-GC-MS) detection weaving material
Expect the method for sensitization aromatic volatile quantity in sample.
Described textile material sample includes but is not limited to routine use with pure cotton material, polyester material, cotton ramie blended spinning material
Expect the textile material product for raw material, preferably textile toy.
Described sensitization aromatic is as shown in the table, totally 48 kinds
The detection method of sensitization fragrance level comprises the following steps in described detection textile material sample,
(1) sample pre-treatments：Textile sample is through acetone ultrasonic extraction, and supernatant liquor crosses 0.22 μm of organic filter membrane of micropore；
(2) in GC-MS determination samples 48 kinds of sensitization aromatic content.
Described sample pre-treatments step is：
(1) textile sample is cut into 5mm × below 5mm fritter with scissors, 0.1g samples (being accurate to 0.001g) are weighed
In 50mL tool plug glass centrifuge tubes, add after 5mL acetone and seal, ultrasonic extraction 15min；
(2) liquid is transferred to 10mL volumetric flasks, then adds 5mL acetone, ultrasonic extraction 15min in the sample；
(3) extract solution is merged into volumetric flask, constant volume is mixed.1mL clear liquids are taken, through 0.22 μm of organic membrane filtration of micropore,
GC-MS is determined.
The step of described GC-MS is determined and parameter are：
Chromatographic column：DB-17MS(30m×0.25mm×0.25μm)；
Injector temperature：250℃；
Column temperature uses temperature programming,
(1) 45 DEG C of initial temperature, retain 2min,
(2) 100 DEG C are risen to 8 DEG C/min,
(3) 150 DEG C are risen to 10 DEG C/min, keep 3min,
(4) 200 DEG C are risen to 8 DEG C/min, keep 5min,
(5) 250 DEG C are risen to 10 DEG C/min, keeps 5min；
Carrier gas：Helium, purity >=99.999%, flow velocity is 1.0mL/min；
Sample introduction pattern：Split sampling, split ratio is 10：1；
Sample size：1μL.
Ion gun (EI) temperature：230℃；
Quadrupole rod temperature：150℃；
Chromatography-mass spectroscopy interface temperature：280℃；
Acquisition mode：Salbutamol Selected Ion Monitoring (SIM), solvent delay：2.8min.
The step of method of described Head space-gas chromatography-mass spectrography (HS-GC-MS) is：0.1g is weighed to prepare
Textile sample in ml headspace bottle, rapid sealing is 23 DEG C and 40 DEG C in head space temperature, equilibration time is GC- under the conditions of 60min
MS methods determine the peak area of sensitization aromatic.
The step of described GC-MS methods and parameter are：
Chromatographic column：DB-17MS(30m×0.25mm×0.25μm)；
Injector temperature：250℃；
Column temperature uses temperature programming,
(1) 45 DEG C of initial temperature, retain 2min,
(2) 100 DEG C are risen to 8 DEG C/min,
(3) 150 DEG C are risen to 10 DEG C/min, keep 3min,
(4) 200 DEG C are risen to 8 DEG C/min, keep 5min,
(5) 250 DEG C are risen to 10 DEG C/min, keeps 5min；
Carrier gas：Helium, purity >=99.999%, flow velocity is 1.0mL/min；
Sample introduction pattern：Split sampling, split ratio is 10：1；
Sample size：1μL.
Ion gun (EI) temperature：230℃；
Quadrupole rod temperature：150℃；
Chromatography-mass spectroscopy interface temperature：280℃；
Acquisition mode：Salbutamol Selected Ion Monitoring (SIM), solvent delay：2.8min.
Brief description of the drawings
Fig. 1, sensitization aromatic gas chromatography-mass spectrum total ion current figure.
Gas chromatography-mass spectrum total ion current figure (the 2A that Fig. 2, the addition of cotton ramie blended spinning matrix are reclaimed：Cotton ramie blended spinning sample is empty
In vain, 2B：Standard adds (10mg/kg)).
Gas chromatography-mass spectrum total ion current figure (the 3A that Fig. 3, the addition of cotton ramie blended spinning matrix are reclaimed：Cotton ramie blended spinning material sample
Blank, 3B：Standard adds (0.01 μ g)).
Fig. 4,10 kinds of typical sensitization aromatic head spaces determine the block diagram of the rate of recovery.
Embodiment
The detection of sensitization aromatic in embodiment 1, weaving toy
Cleaning Principle
Assay：Textile sample is through acetone ultrasonic extraction, and supernatant liquor crosses 0.22 μm of organic filter membrane of micropore, and GC-MS is surveyed
It is fixed.
Volatile quantity is determined：Textile sample is cut into small pieces, is placed in ml headspace bottle, rapid sealing, HS-GC-MS is determined.
Instrument, reagent and material
Key instrument：
Agilent 7890-5975C gas chromatograph-mass spectrometers (match somebody with somebody EI ion guns, U.S. Aglient Techlogies are public
Department, with Combi-xt PAL Multifunctional sample injection devices, CTC companies of Switzerland)；
Head-space sampler (Aglient Techlogies companies of the U.S., 7697A)；
HS-260 types oscillator (German IKA companies)；
The basic model vortex mixers of MS 3 (German IKA companies)；
XS205 balances (Mettler-Toledo companies)；
Numerical control supersonic (KQ-500DE, Kunshan Ultrasonic Instruments Co., Ltd.)；
Liquid-transfering gun (10-100 μ L, 20-200 μ L, 100-1000 μ L, 500-5000 μ L, Eppendorf companies).
Main agents and material：
Acetone, ethanol, methanol (chromatographically pure, German Merke companies)；
48 kinds of sensitization aromatic standard items (concrete condition is shown in Table 1), by German Dr.Ehrenstorfer GmbH companies and
Sigma-Aldrich provides, except radia heleii oily (Alanroot oil, 97676-35-2), hydroabietyl alcohol
(Hydroabietyl alcohol, 13393-93-6), ethyl acrylate (Ethyl acrylate, 140-88-5), 4- (4- first
Phenyl) -3- butene-2s -one (4- (p-Methoxyphenyl) -3-butene-2-one, 943-88-4), benzylalcohol
(Benzyl alcohol, 100-51-6) is that remaining standard items is standard substance, and purity is big outside 1000mg/L standard liquids
In 95.0%.
The preparation of standard liquid：
Appropriate each standard items are accurately weighed respectively,
(1) Standard Stock solutions that concentration is 1000mg/L are made into acetone, are saved backup in refrigerator at -18 DEG C；
Appropriate Standard Stock solutions are accurately pipetted, are made into suitable solvent such as acetone or ethanol or methanol concentration is 10mg/L
Hybrid standard intermediate solution, accurately pipettes interstitial fluid in the standard, is diluted step by step with suitable solvent, obtains sensitization aromatic series
Hybrid standard working solution.
(2) with 12 kinds of sensitization aromatic mixed standard solutions that acetone compound concentration is 100mg/L, the solution is used to prepare
Positive.12 kinds of sensitization aromatic are ethyl acrylate (Ethyl acrylate), trans -2- hexenoic aldehydes (trans-2-
Hexenal), linalool (Linalool), methyl 2-octynoate (Methyl heptine carbonate), 4-TBP
(4tert-Butylphenol), eugenol (Eugenol), dihydrocoumarin (Dihydrocoumarin), cumarin
(Coumarin), diphenylamines (Diphenylamine), jasminal (Amyl cinnamal), 1- (4- anisyls)-
1- penten-3-ones (1- (p-Methoxyphenyl-1-penten-3-one), benzyl cinnamate (Benzyl cinnamate).
It is prepared by positive
Because sensitization aromatic has limitednumber in commercially available weaving toy sample, content is different, positive with these
The situation for not being suitable for tens kinds of sensitization fragrance level analyses, therefore, this research root occurs in the experimental method of sample optimization
The requirement limited the quantity according to sensitization aromatic, according to material the most frequently used in the market weaving toy, is prepared for 3 kinds of representative weavings and plays
Has the positive of material (pure cotton, terylene, cotton ramie blended spinning), preparation process is：Weigh 0.1g pure cotton, terylene and cotton ramie blended spinning
Material, is separately added into 1mL 10mg/kg standard liquid liquid, immersion, treats that solvent evaporates into the nearly dry i.e. obtained aromatic containing sensitization
Positive.
Sample pre-treatments
Assay：
(1) textile sample is cut into 5mm × below 5mm fritter with scissors, 0.1g samples (being accurate to 0.001g) are weighed
In 50mL tool plug glass centrifuge tubes, add after 5mL acetone and seal, ultrasonic extraction 15min,
(2) liquid is transferred to 10mL volumetric flasks, then adds 5mL acetone in the sample, ultrasonic extraction 15min,
(3) extract solution is merged into volumetric flask, constant volume is mixed.1mL clear liquids are taken, through 0.22 μm of organic membrane filtration of micropore,
GC-MS is determined.
Volatile quantity is determined：
(1) textile sample that 0.1g prepares is weighed in ml headspace bottle, and rapid sealing is 23 DEG C and 40 in head space temperature
DEG C, equilibration time is measure under the conditions of 60min.
Annotation：Normal children can play with toys at room temperature, and (40 DEG C of highest) plays with toys when extreme case is such as had a bath, therefore
This experiment have chosen investigate ambient operation condition (23 DEG C) and extremely under bad operating condition (40 DEG C) in textile aromatic volatilization
Situation.
GC-MS conditions
Chromatographic column：DB-17MS(30m×0.25mm×0.25μm)；
Injector temperature：250℃；
Column temperature uses temperature programming,
45 DEG C of initial temperature, retains 2min,
100 DEG C are risen to 8 DEG C/min, 150 DEG C are risen to 10 DEG C/min, 3min is kept,
200 DEG C are risen to 8 DEG C/min again, 5min is kept,
It is last to rise to 250 DEG C with 10 DEG C/min, keep 5min；
Carrier gas：Helium, purity >=99.999%, flow velocity is 1.0mL/min；
Sample introduction pattern：Split sampling, split ratio is 10：1；Sample size is 1 μ L.
Ion gun (EI) temperature：230℃；
Quadrupole rod temperature：150℃；
Chromatography-mass spectroscopy interface temperature：280℃；
Acquisition mode：Salbutamol Selected Ion Monitoring (SIM),
Solvent delay：2.8min；Other Mass Spectrometry Conditions are shown in Table 1.
The Mass Spectrometry Conditions and CAS of the sensitization aromatic assay method of table 1
The optimization of chromatographic condition
Sensitization aromatic species is various, when being analyzed using gas-chromatography, if instrumental conditions are improper, easily goes out
The situation that existing different compound chromatographic peaks are overlapped, therefore, must be optimized to gas-chromatography separation condition.Using HP-5MS or
When DB-5MS chromatographic columns are analyzed, compound appearance is early, and many compound separation are incomplete, and for qualitative ion complete one
The isomer 7- methylcoumarins (7-Methylcoumarin) and 6-Methylcoumarin (6-Methylcoumarin) of cause,
Its chromatogram peak complete-superposing, it is impossible to separate, it is consistent with result by references；And when using DB-Wax isopolarity posts, due to its heat-resisting temperature
Spend for 250 DEG C -260 DEG C, and the compound such as benzyl salicylate and benzyl cinnamate (boiling point is 300 DEG C) goes out in this chromatographic column
Peak is very late, it is necessary to which the column length time is in the condition of high temperature, and this destroys very big to chromatographic column, and many column bleeds occur；
And when selecting DB-17MS chromatographic columns, using split sampling pattern, each compound peak shape is good, separating effect is also good, and 7- methyl is fragrant
Legumin and 6-Methylcoumarin can be separated, therefore, this method selection DB-17MS.Temperature programming condition is：45 DEG C of initial temperature,
Retain 2min, 100 DEG C are risen to 8 DEG C/min, 150 DEG C are risen to 10 DEG C/min, keep 3min, then 200 are risen to 8 DEG C/min
DEG C, 5min is kept, finally 250 DEG C are risen to 10 DEG C/min, 5min is kept.
The optimization of Mass Spectrometry Conditions
Under above-mentioned chromatographic condition, there are 4 pairs of Compound Retention times and approach, be respectively：4- metoxyphenols
(14.02min) and laurine (14.08min), 2,4- dihydroxy -3- tolyl aldehydes (19.80min) and pseudoionone
(19.99min), 7- methylcoumarins (22.34min) and lyral (22.38min), a- jasminolenes (23.25min)
With 4- (4- methoxyphenyls) -3- butene-2s -one (23.32min), but by select fragment misaligned in each pair compound from
Son carries out selection ion qualitative and quantitative analysis, it is ensured that when SIM modes are scanned, each pair compound is efficiently separated.By above-mentioned
Optimal conditions, selection electron impact ion source (EI), drainage pattern gathers, 48 kinds of sensitization aromatic is entered simultaneously for SCAN/SIM
Row analysis, the retention time and characteristic ion for obtaining each compound is as shown in table 1, and gas chromatography-mass spectrum total ion current figure is as schemed
1。
The optimization of dissolving-ultrasonic extraction
The selection of solvent
The present invention have chosen acetone, methanol, 3 kinds of solvents of ethanol and carries out extraction efficiency contrast respectively, the results are shown in Table 2.Self-control
Positive, wherein No. 1 sample is pure cotton sample；No. 2 samples are terylene sample；No. 3 samples are linen-cotton sample.In positive
The theoretical content of 12 kinds of representative sensitization aromatic is 100mg/kg.
Many experiments result is found, with the rate of recovery scope of acetone extraction between 69.2%-103.1%, is carried with methanol
The rate of recovery scope taken is between 43.4%-101.8%, and with the rate of recovery of acetone extraction in addition to individual compound, substantially
All it is that more than 85%, and the rate of recovery extracted with methanol is except indivedual outer, most of all below 90%, the recovery of ethanol extraction
Rate is basic between acetone and methanol.Therefore, for this experiment, acetone is significantly better than methanol and ethanol, and recovering effect is more
It is good.
The selection of ultrasonic time
Many articles point out that the length of ultrasonic power and time have a certain impact to the rate of recovery.This research selection is each
Ultrasonic 15min, is repeated twice and direct ultrasound two kinds of conditions of 30min have carried out rate of recovery checking, the results are shown in Table 2.Self-control is positive
Sample, wherein No. 1 sample is pure cotton sample；No. 2 samples are terylene sample；No. 3 samples are linen-cotton sample.
Found by ultrasound contrast, ultrasound 15min ratios are distinguished twice, and once the ultrasound 30min rate of recovery is higher.Therefore, this hair
Ultrasound 15min mode is distinguished in bright selection twice.
To sum up result considers, the present invention is from acetone as dissolving ultrasound is extracted twice, and each 15min mode is as preceding
Treatment conditions carry out subsequent experimental.
As can be seen from Table 2, ethyl acrylate rate of recovery in pure cotton sample, terylene sample and linen-cotton sample is changed with respect to other
Compound is relatively low, this should be because this compound volatility of ethyl propionate it is stronger, make positive when volatilization loss compared with
It is many.
The rate of recovery of the 2 12 kinds of sensitization aromatic of table under different solvents, different ultrasonic powers
The linear relationship and detection limit of method
Extraction standard solution is prepared using pure cotton, terylene and cotton ramie blended spinning matrix blank extract solution, with same concentration neat solvent
Standard liquid is while sample introduction, as a result shows, the matrix effect of above-mentioned sample does not have influence substantially, therefore, and this part experiment is also used
Solvent standard curve is quantified：By 0.1,0.2,0.4,0.8,1.0,2.0,4.0 and 8.0mg/L hybrid standard working solution sample introductions
Analysis, standard curve is made with mass concentration and peak area.As a result show, fanesol and lyral in 1~8mg/L, it is trans-
2- heptenals, citronellol, methyl 2-octynoate, geraniol, citral, para-methoxybenzyl alcohol, cinnamyl alcohol, pseudoionone, amyl group
Cinnamyl alcohol is in 0.2~8mg/L, and remaining 38 kinds of aromatic has good linear relationship, phase relation in the range of 0.1~8mg/L
Number is 0.9962~0.9999.The detection limit (S/N≤3) of method is 6mg/kg (lyral is 15mg/kg), quantitative limit (S/N
≤ 10) it is 20mg/kg (FARNESOL and lyral are 50mg/kg).
The rate of recovery and precision of method
In view of positive is preferable (concrete outcome is shown in Table 3) in MRL (100mg/kg) rate of recovery experimental result, this research will
Addition concentration is set as 50mg/kg (near quantitative limit), and recovery experiment is added by taking cotton ramie blended spinning as an example, 3, cotton are the results are shown in Table
Numb blending matrix blank and standard addition total ion current figure are shown in Fig. 2.As known from Table 3, sensitization aromatic is in above-mentioned cotton ramie blended spinning material
It is 81.1%~107.3% in the recovery of standard addition of 50mg/kg concentration, relative standard deviation is 2.4%~8.7% in material.
The rate of recovery and relative standard deviation of the method for table 3
The release of sensitization aromatic in textile material toy
This research is measured using Head space to 12 kinds in textile toy typical sensitization aromatic burst sizes：Weigh
0.1g positives (by taking cotton ramie blended spinning material as an example) are in ml headspace bottle, rapid sealing, are respectively 23 DEG C and 40 DEG C in temperature, put down
The weighing apparatus time is the peak area of measure sensitization aromatic under the conditions of 60min, and Fig. 3 is shown in cotton ramie blended spinning matrix blank and standard addition.With
Based on the standard items amount of addition, by the calculated by peak area rate of recovery of burst size, its unlike material releasing at different temperatures
High-volume (it is converted to the rate of recovery) and sees Fig. 4.As can be seen from Figure 4, under the conditions of 40 DEG C, the volatile quantity of the compound detected is than 23 DEG C
Under the conditions of it is big.Wherein, ethyl acrylate, benzyl cinnamate are not detected, according to aromatic with different temperatures volatilization Journal of Sex Research
Result show that ethyl acrylate is readily volatilized because of its, can't detect when the overwhelming majority is lost in preparation process, and meat
Benzyl cinnamate needs the comparative high temperature could to volatilize；The compounds such as linalool, methyl 2-octynoate are larger in 40 DEG C of volatile quantities；But
It is that compared with adding experiment, these aromatic are not all evaporated all, and maximum volatile quantity is only the 27.2% of content.
The measure of sensitization aromatic burst size in textile toy is carried out using head space method, to actual children suction, licks and licks what is caused
Aromatic intake has practical significance.
Actual sample is detected
The detection method set up using the present embodiment, the textile material toy common in the market has carried out examination inspection
Survey.Project team's stochastic buying toys samples from the market.
Configuration 0.2,0.5,0.8,1.0,2.0,4.0,8.0, the analysis of 10.0mg/L hybrid standard working solutions sample introduction, with matter
Amount concentration makees standard curve with peak area, and detection positive the results are shown in Table 4.
The compound and concentration detected in the market of table 4 purchase textile material toy
After testing, micro sensitization flavouring agent is detected in 3 kinds of toys, its mark without departing from 100mg/kg as defined in EC regulations
Show limit value.Illustrate in the market part toy it is different degrees of mixed with sensitization aromatic, although the compound detected at present exists
As defined in European Union in the range of 11 kinds that 100mg/kg needs sign, but it is limited due to collecting sample scope, however not excluded that other
The detection of more disabling aromatic is had in toy.
Finally it should be noted that above example only helps skilled in the art to understand the essence of the present invention, not
It is used as limiting the scope of the present invention.
Claims (8)
1. the side of sensitization fragrance level in a kind of method detection textile material sample of gas chromatography-mass spectrography (GC-MS)
Method, it is characterised in that comprise the following steps：
(1) sample pre-treatments：Textile sample is through acetone ultrasonic extraction, and supernatant liquor crosses the organic filter membrane of micropore；
(2) in GC-MS determination samples 48 kinds of sensitization aromatic content.
2. according to the method described in claim 1, it is characterised in that described textile material sample is including but not limited to daily
Use using pure cotton material, polyester material, cotton ramie blended spinning material as the textile material product of raw material, preferably textile toy.
3. method according to claim 1 or 2, it is characterised in that totally 48 kinds of described sensitization aromatic, table specific as follows
It is shown,
4. method according to claim 3, it is characterised in that described sample pre-treatments step is：
(1) textile sample is cut into 5mm × below 5mm fritter with scissors, weigh 0.1g samples (being accurate to 0.001g) in
In 50mL tool plug glass centrifuge tubes, add after 5mL acetone and seal, ultrasonic extraction 15min；
(2) liquid is transferred to 10mL volumetric flasks, then adds 5mL acetone, ultrasonic extraction 15min in the sample；
(3) extract solution is merged into volumetric flask, constant volume mixes, 1mL clear liquids taken, through 0.22 μm of organic membrane filtration of micropore.
5. method according to claim 4, it is characterised in that the step of described GC-MS is determined and parameter are：
Chromatographic column：DB-17MS(30m×0.25mm×0.25μm)；
Injector temperature：250℃；
Column temperature uses temperature programming,
(1) 45 DEG C of initial temperature, retain 2min,
(2) 100 DEG C are risen to 8 DEG C/min,
(3) 150 DEG C are risen to 10 DEG C/min, keep 3min,
(4) 200 DEG C are risen to 8 DEG C/min, keep 5min,
(5) 250 DEG C are risen to 10 DEG C/min, keeps 5min；
Carrier gas：Helium, purity >=99.999%, flow velocity is 1.0mL/min；
Sample introduction pattern：Split sampling, split ratio is 10：1；
Sample size：1μL.
Ion gun (EI) temperature：230℃；
Quadrupole rod temperature：150℃；
Chromatography-mass spectroscopy interface temperature：280℃；
Acquisition mode：Salbutamol Selected Ion Monitoring (SIM), solvent delay：2.8min.
6. sensitization virtue in a kind of method detection textile material sample of Head space-gas chromatography-mass spectrography (HS-GC-MS)
The method of pastil volatile quantity, it is characterised in that comprise the following steps：0.1g textile samples are weighed in ml headspace bottle, rapid sealing,
It it is 23 DEG C and 40 DEG C in head space temperature, equilibration time is the peak area of GC-MS methods measure sensitization aromatic under the conditions of 60min.
7. method according to claim 6, it is characterised in that described textile material sample is including but not limited to daily
Use using pure cotton material, polyester material, cotton ramie blended spinning material as the textile material product of raw material, preferably textile toy；Institute
The sensitization aromatic stated is 48 kinds of sensitization aromatic described in claim 3.
8. the method according to claim 6 or 7, it is characterised in that the step of described GC-MS methods and parameter is：
Chromatographic column：DB-17MS(30m×0.25mm×0.25μm)；
Injector temperature：250℃；
Column temperature uses temperature programming,
(1) 45 DEG C of initial temperature, retain 2min,
(2) 100 DEG C are risen to 8 DEG C/min,
(3) 150 DEG C are risen to 10 DEG C/min, keep 3min,
(4) 200 DEG C are risen to 8 DEG C/min, keep 5min,
(5) 250 DEG C are risen to 10 DEG C/min, keeps 5min；
Carrier gas：Helium, purity >=99.999%, flow velocity is 1.0mL/min；
Sample introduction pattern：Split sampling, split ratio is 10：1；
Sample size：1μL.
Ion gun (EI) temperature：230℃；
Quadrupole rod temperature：150℃；
Chromatography-mass spectroscopy interface temperature：280℃；
Acquisition mode：Salbutamol Selected Ion Monitoring (SIM), solvent delay：2.8min.
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Cited By (1)
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| CN114034848A (en) * | 2021-11-23 | 2022-02-11 | 通标标准技术服务有限公司 | Method for measuring allergic aromatic in plastic toy |
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