CN103837617B - Method for analyzing migration volume from photoinitiator to modified polyphenylene oxide (MPPO) in printed wrapping paper based on liquid chromatograph-tandem mass spectrometer (LC-MS/MS) technology - Google Patents

Abstract

The invention discloses a method for analyzing migration volume from a photoinitiator to modified polyphenylene oxide (MPPO) in printed wrapping paper based on a liquid chromatograph-tandem mass spectrometer (LC-MS/MS) technology. The method is characterized by comprising the following steps: adsorbing a photoinitiator target, which is released by a sample under simulated conditions, through MPPO, performing solvent extraction on MPPO by using acetonitrile, concentrating and filtering the supernatant, and measuring the specific migration volume of the photoinitiator in the printed packaging material through the LC-MS/MS technology. According to the method, the LC-MS/MS is selected as the detection means, has higher interference resistance compared with primary mass spectrum (MS) and has higher sensitivity and selectivity, the false positive detection result can be greatly reduced, and the requirement on sample pretreatment is low. The method can rapidly and accurately detect the specific migration volume of the photoinitiator in the printed packaging material, the measurement result is accurate, and repeatability is high.

Description

Based on light trigger in LC-MS/MS technical Analysis printed wrapper to the method for MPPO migration amount

Technical field

The invention belongs to the detection technique field of light trigger Special migration in printed apcksging material, relate generally to 2-hydroxy-2-methyl-1-phenylacetone in printed apcksging material, benzophenone, methyl benzophenone, p-N, N-dimethyl ethyl aminobenzoate, 2,2-dimethoxy-2-phenyl acetophenone, methyl o-benzoylbenzoate, EHA, 2-methyl isophthalic acid-(4-methyl mercapto) phenyl 2-morpholinyl-1-acetone, isopropyl thioxanthone, xenyl Benzophenone, 2,4-diethyl thioxanthone, two (dimethylamino) benzophenone of 4,4-, two (diethylamino) benzophenone of 4,4-, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, the determination techniques of the Special migration of 15 kinds of light triggers such as 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-acetone, be a kind of be specifically analogies with Noryl, under certain migration experiment condition, migration experiment is carried out to printed apcksging material, light trigger in the wrappage adsorbed by acetonitrile extraction analogies Noryl (MPPO), and carry out method for measuring with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS).

Background technology

Along with popularizing of UV typography, light trigger (Photoinitiators, PIs) is widely used in packages printing as the principal ingredient of UV curable ink ^[1,2].Light trigger is the compound that a class has photosensitive group, can produce free radical, kation etc. under the exciting of ultraviolet light, and trigger monomer polymerization crosslinking solidifies.Research in recent years finds, after UV printing-ink has solidified, wherein residual ultraviolet initiator under certain conditions, chemical transport can occur or pollute the food in packaging by physical contact, thus cause potential hazard to the health of human body ^[3].

Light trigger is polluted by chemical transport or physical contact and pollutes food, relevant toxicologic study also proves that light trigger produces adverse influence to health, in order to control the use of light trigger, European and American countries promulgates the use of regulation and permission log restriction light trigger in succession.2005, Swiss Confederation domestic affairs portion (FDHA) promulgated RS 817.023.21 decree, and the V part of this decree annex 6 defines the light trigger material in 96 kinds of permission to use printing-inks, and defined (SML) requirement of its specific transfer limitation ^[4]., the few members state Res AP(2002 in European Union " about intending and the paper and paperboard material of Food Contact and goods " in 2007) resolve in 1, clearly prohibit the use Michler's keton light trigger, require that its SML is less than 0.01 mg/kg simultaneously ^[5].In March, 2009 European Union's food chain and animal health standing committee (EFSA) formulated the maximum migration limitation of printing-ink packaging for foodstuff, the 4-methyl benzophenone in regulation packaging for foodstuff printing-ink material and the total migration ultimate value (SML (T)) of benzophenone must lower than 0.6 mg/kg ^[6].2010, printing-ink association of European Union (EuPIA) is for the PIs in printing ink and promulgated " low migration UV light trigger permission to use list ", and the respective specified SML of various low migration light trigger ^[7].

For the packaging material for food contacted with dry food, because they are different from the migration medium of food liquid, the specific transfer method of European Union's suggestion adopts Noryl (MPPO) as food simulants, and the actual serviceability temperature of reference food contact material and duration of contact carry out specific transfer experiment ^[8].2003, European Union EN 14338-2003 " intend the paper and Board of Food Contact---do analogies with improvement polyphenylene oxide and measure condition from paper and paperboard migration " transition condition of paper and Board and method are specified, namely adopt 1 dm ²paper and paperboard material, at specific temperature and transit time condition, carry out migration experiment with 4 g MPPO, then with organic solvent, the corresponding analytical approach of rear employing extracted to MPPO and detect Special migration.But this standard is the reference template proposing MPPO migration experiment general, does not propose suitable detection method for specific target analytes.And this standard has only related to the part of migration experiment, follow-up detection means and method are not also instructed.

At present, about the analytical approach of light trigger mainly comprises GC-MS(gas chromatography-mass spectrography), liquid phase chromatography and liquid chromatography tandem mass spectrometry ^[9], the light trigger related to mainly comprises isopropyl thioxanthone (ITX), benzophenone (BP), 4-methyl benzophenone (4-BP) etc. ^[10-12], but the report of multiple light trigger assay method is few.In the technique that UV printing is actual, in order to make up the shortcoming of various light trigger in UV ink, improving light-initiated efficiency and expanding its usable range, need in a lot of situation multiple light trigger with the use of.Along with various circles of society's carrying out in a deep going way the raising of the degree of concern of light trigger and relevant toxicologic study, eager needs a kind ofly quick, high-throughout method can be used for the determination and analysis of the Special migration of light trigger.At present, domestic research mainly concentrates on light-initiated residual detection in food or wrappage, seldom relate to light trigger specific transfer quantitative analysis in dry food, more do not utilize MPPO as the report of analogies to light trigger specific transfer analysis method.

Although gas chromatography tandem mass spectrometry has good advantage in light trigger is qualitative, in the analysis of the photoinitiator compound that liquid chromatography technology is high at some boiling points, polarity is comparatively strong, molecular weight is larger, there is more significant advantage.Because the limitation of most of light trigger is lower, the limitation of some is at 0.01 μ g/g, and the sensitivity therefore improving method is very important.

Summary of the invention

The present invention is intended to by LC-MS/MS technology, set up the specific transfer analysis method of light trigger in high flux, high-sensitive printed apcksging material, thus to measure for the SML of light trigger in printed apcksging material and safety evaluation provides and detects analytical technology support.The present invention selects LC-MS/MS as detection means, and versus primary mass spectrum (MS) its antijamming capability is stronger, has higher sensitivity and selectivity, can greatly reduce false-positive testing result, lower to the requirement of sample pre-treatments.Quick, the accurate Special migration detecting light trigger in printed apcksging material of the method energy, measurement result is accurate, reproducible.

The object of the invention is to be achieved through the following technical solutions:

A kind of based on light trigger in LC-MS/MS technical Analysis printed wrapper to the method for MPPO migration amount, that the light trigger object that discharges under simulated conditions of a kind of sample is after Noryl MPPO adsorbs, with acetonitrile, solvent extraction is carried out to MPPO, filter the method measuring light trigger Special migration in printed apcksging material with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) after supernatant concentration, concrete steps are as follows:

A, preparation of samples: take MPPO, evenly tiling is to moving apparatus, and will be laid in above MPPO after the cutting of wrapping paper sample, Noryl MPPO with the input ratio of wrapping paper sample be: the corresponding 0.25dm of 1g Noryl MPPO ²wrapping paper sample area, pending migration experiment after sealing moving apparatus, described moving apparatus is tool lid double dish or tool plug measuring cup that can be airtight.

B, migration experiment: according to practical study and test needs, moving apparatus is positioned in baking oven and carries out migration experiment with uniform temperature heating certain hour, actual temp and time are determined with reference to virtual package storage condition, temperature is generally in room temperature to 70 DEG C, more than 5 minutes time, take out and be cooled to room temperature;

C, oscillation extraction: transferred to by the MPPO in moving apparatus in tool plug centrifuge tube, add the acetonitrile of certain volume, with speed vortex oscillation 10 min of 2000 r/min on vortex oscillation instrument, then with centrifugal 5 min of 8000 r/min; The ratio 10ml:1g of acetonitrile solvent volume used and Noryl quality during extraction.

D, concentrated: the extract getting 1-4 mL is placed on Nitrogen evaporator and is concentrated into 1mL, after 0.22 μm of organic phase membrane filtration, carry out LC-MS/MS analysis;

The configuration of e, extraction standard working solution: take 0.05 g(respectively and be accurate to 0.1 mg) various light trigger sterling, be placed in 10 mL volumetric flasks, dissolve and constant volume with acetonitrile, be mixed with the single standard solution that concentration is 5 mg/mL; Then be made into the acetonitrile solution of mixed standard solution, and be finally mixed with the standard working solution of the various light triggers of the pure acetontrile with concentration gradient; Take blank MPPO, repeat c, Step d, after concentrated for extract drying up, then redissolve with the standard working solution of pure acetontrile, be finally mixed with the extraction standard working solution of the various light triggers with same concentration gradient;

The manner of formulation of extraction standard working solution is as follows: take 0.05 g(respectively and be accurate to 0.1 mg) various light trigger sterling, be placed in 10 mL volumetric flasks, dissolve and constant volume with acetonitrile, be mixed with the list mark that concentration is 5 mg/mL; Respectively often kind of single standard is really pipetted 1 mL, be placed in 50mL volumetric flask, with acetonitrile constant volume, be mixed with the mixed standard solution I that each target concentration is 100 μ g/mL; Then accurately pipette 1 mL mixed standard solution I, be placed in 10 mL volumetric flasks, use acetonitrile constant volume, be mixed with the mixed standard solution II that each target concentration is 1 μ g/mL;

The preparation of extraction standard solution I: the mixed standard solution I accurately pipetting 0.01 mL, 0.02 mL, 0.05 mL, 0.10 mL and 0.20 mL, with acetonitrile constant volume in 10 mL, obtains the series standard working solution of neat solvent preparation.Take blank MPPO, repeat c, Step d, after concentrated for 1mL extract drying up, then redissolve with the standard working solution of the pure acetontrile of 1mL, matrix series standard solution I concentration of final preparation is: 100 ng/mL, 200 ng/mL, 500 ng/mL, 1000 ng/mL, 2000 ng/mL.

The preparation of extraction standard solution II: the mixed standard solution II accurately pipetting 0.01 mL, 0.02 mL, 0.05 mL, 0.10 mL and 0.20 mL, with acetonitrile constant volume in 2.5 mL, obtains the series standard working solution of neat solvent preparation.Take blank MPPO, repeat c, Step d, after concentrated for 4 mL extracts drying up, redissolve with the standard working solution of the pure acetontrile of 1mL, matrix series standard solution II concentration of final preparation is: 4 ng/mL, 8 ng/mL, 20 ng/mL, 40 ng/mL, 80 ng/mL, 200 ng/mL again.

F, LC-MS/MS measure: the extraction standard working solution drawing the variable concentrations prepared, and after crossing 0.22 μm of organic filter membrane, inject LC-MS/MS and analyze;

The calculating of h, result: join with matrix the quantitative test that mark external standard method carries out light trigger object, namely with the secondary Selective ion mode peak area of light trigger, regretional analysis is carried out to its respective concentration, obtain typical curve; Sample after extracting is measured, records the secondary Selective ion mode peak area of light trigger, substitute into typical curve, try to achieve the Special migration of light trigger in sample; Final migration amount result is with migration amount (the i.e. mg/dm of unit area packaging light trigger ²) or unit mass Noryl in light trigger content (mg/kg) meter.

In the present invention, the liquid phase chromatogram condition of employing is: chromatographic column: Luna PFP (2) (150 mm × 4.6 mm, 3 μm, Phenomenex company of the U.S.); Mobile phase: acetonitrile/0.1% aqueous formic acid, flow velocity: 500 μ L/min; Gradient elution program is in table 1; Column temperature: 30 DEG C; Sample size: 10 μ L; The Mass Spectrometry Conditions adopted: scan mode: positive ion scans; Electric spray ion source (ESI); Atomization gas flow is 50 psi; Gas curtain airshed 15 psi; Auxiliary heating airshed is 50 psi; Ionization temperature 500 DEG C; Impinging air flows amount is 10 psi; 4 kinds of gases are nitrogen; The residence time is 50 msec; Ionization voltage 5500 V, detection mode: positive ion polyion reaction monitoring (MRM), the retention time of light trigger and MRM parameter are in table 2, and chromatogram is shown in Fig. 3.

table 1 liquid chromatogram mobile phase composition, flow velocity and graded

table 2 light trigger object and interior target retention time and MRM parameter

The invention provides the analytical approach method of light trigger Special migration in a kind of high flux, highly sensitive mensuration wrappage.Compared with prior art the inventive method has following excellent results:

(1) the inventive method is first based on the migration amount of 15 kinds of light triggers in Liquid Chromatography-Tandem Mass Spectrometry technical Analysis printed apcksging material to Noryl analogies.

(2) the present invention adopts acetonitrile as the extract extracting light trigger in MPPO, the high base affection brought when also reducing acetone extract while high relative to extraction efficiency acetone and other organic solvent, the machine solution of making is cleaner, decreases instrument maintenance in use.

(3) present invention optimizes migration experiment condition, adopt less Noryl Migration Simulation thing, thus greatly reduce check analysis cost.

The LC-MS/MS that the inventive method have employed high sensitivity and strong anti-interference ability detects, therefore there is the advantage that operation is accurate, highly sensitive and reproducible, the detectability of object can be made greatly to reduce, reduce the requirement to sample purification simultaneously, thus simplify pretreatment process.

Accompanying drawing explanation

Fig. 1 is assay method process flow diagram of the present invention;

Fig. 2 is migration Experimental equipment (two vessel represent the test specimen of different value respectively);

Fig. 3 is LC-MS/MS chromatogram;

In Fig. 3: 1,2959,2,369,3,1173,4,907,5, OMBB, 6, BDK, 7, MK, 8, BP, 9, EDB, 10,2-MBP, 11, DEAB, 12, PBZ, 13,2-ITX, 14, EHDBA, 15, DETX.

Embodiment

The present invention is described further below in conjunction with example, but is not restriction the present invention.

Example 1:

1. instrument and reagent:

15 kinds of light triggers: 2-hydroxy-2-methyl-1-phenylacetone, benzophenone, 2 methyl benzophenone, p-N, N-dimethyl ethyl aminobenzoate, 2, 2-dimethoxy-2-phenyl acetophenone, methyl o-benzoylbenzoate, EHA, 2-methyl isophthalic acid-(4-methyl mercapto) phenyl 2-morpholinyl-1-acetone, 2-isopropyl thioxanthone, xenyl Benzophenone, 2, 4-diethyl thioxanthone, 4, two (dimethylamino) benzophenone of 4-, 4, two (diethylamino) benzophenone of 4-, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-acetone, be analysis pure, acetonitrile, acetone, methyl alcohol, be chromatographic grade reagent, distilled water, meets the requirement of one-level water in GB/T 6682, Noryl (MPPO), 60 order ~ 80 orders.

API 4000 quadrupole rod tandem mass spectrometer; Switzerland Mettler AE 163 electronic balance (sensibility reciprocal: 0.0001g); Shanghai ESPEC company LC-213 baking oven; U.S. Troemner company's T ALBOYS turbula shaker; Germany Sigma 3-30k high speed freezing centrifuge.

2. sample preparation:

Take about 4g MPPO, evenly tiling is to moving apparatus, and wrapping paper sample is cut into 1dm ²after, be laid in above MPPO, pending migration experiment after sealing moving apparatus.According to practical study and test needs, be positioned over by moving apparatus with 70 DEG C of heating 2 h in baking oven, taking-up is cooled to room temperature.

MPPO in double dish is transferred in tool plug centrifuge tube, add the acetonitrile of certain volume, with speed vortex oscillation 10 min of 2000 r/min on vortex oscillation instrument, then with centrifugal 5 min of 8000 r/min; Pipette a certain amount of extract and be concentrated into 1 mL, after 0.22 μm of organic phase membrane filtration, carry out LC-MS/MS analysis.

3. prepare extraction standard working solution:

Take 0.05 g(respectively and be accurate to 0.1 mg) various light trigger sterling, be placed in 10 mL volumetric flasks, dissolve and constant volume with acetonitrile, be mixed with the list mark that concentration is 5 mg/mL; Respectively often kind of single standard is really pipetted 1 mL, be placed in 50mL volumetric flask, with acetonitrile constant volume, be mixed with the mixed standard solution I that each target concentration is 100 μ g/mL; Then accurately pipette 1 mL mixed standard solution I, be placed in 10 mL volumetric flasks, use acetonitrile constant volume, be mixed with the mixed standard solution II that each target concentration is 1 μ g/mL;

The preparation of extraction standard solution I: the mixed standard solution I accurately pipetting 0.01 mL, 0.02 mL, 0.05 mL, 0.10 mL and 0.20 mL, with acetonitrile constant volume in 10 mL, obtains the series standard working solution of neat solvent preparation.Take blank MPPO, repeat c, Step d, after concentrated for 1mL extract drying up, then redissolve with the standard working solution of the pure acetontrile of 1mL, matrix series standard solution I concentration of final preparation is: 100 ng/mL, 200 ng/mL, 500 ng/mL, 1000 ng/mL, 2000 ng/mL.

The preparation of extraction standard solution II: the mixed standard solution II accurately pipetting 0.01 mL, 0.02 mL, 0.05 mL, 0.10 mL and 0.20 mL, with acetonitrile constant volume in 2.5 mL, obtains the series standard working solution of neat solvent preparation.Take blank MPPO, repeat c, Step d, after concentrated for 4 mL extracts drying up, then redissolve with the standard working solution of the pure acetontrile of 1mL, matrix series standard solution II concentration of final preparation is: 4 ng/mL, 8 ng/mL, 20 ng/mL, 40 ng/mL and 80 ng/mL.

4. assay method:

The standard working solution of the variable concentrations prepared is injected LC-MS/MS, carries out quantitative test with external standard method, namely with the secondary Selective ion mode peak area of light trigger object, regretional analysis is carried out to its respective concentration, obtain typical curve; Sample after extracting is measured, records the secondary Selective ion mode peak area detecting light trigger, substitute into typical curve, try to achieve the Special migration of the light trigger in sample.

When LC-MS/MS measures, the liquid phase chromatogram condition of employing is: chromatographic column: Atiantis dC18 (150 mm × 2.1 mm, 3 m, Waters, US); Mobile phase: acetonitrile/0.1% aqueous formic acid, flow velocity: 500 μ L/min; Gradient elution program is in table 1; Column temperature: 30 DEG C; Sample size: 10 μ L; The Mass Spectrometry Conditions adopted: scan mode: positive ion scans; Electric spray ion source (ESI); Atomization gas flow is 50 psi; Gas curtain airshed 15 psi; Auxiliary heating airshed is 50 psi; Ionization temperature 550 DEG C; Impinging air flows amount is 10 psi; 4 kinds of gases are nitrogen; The residence time is 50 msec; Ionization voltage 5500 V, detection mode: positive ion polyion reaction monitoring (MRM), light trigger and interior target retention time and MRM parameter are in table 2.

5. method evaluation:

1. the detectability of method:

The standard working solution of variable concentrations light trigger is injected LC-MS/MS, detectability (LOD) is calculated with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), and with 10 times of signal to noise ratio (S/N ratio) (S/N=10) calculation in quantities limit detectability (LOQ), consider the acceptability of recovery result simultaneously, the detection limit of final preparation method and quantitative limit, in table 3.Result shows that the detectability of all compounds is between 0.001 mg/kg ~ 0.021 mg/kg, illustrates that the sensitivity of this method is higher.The limitation requirement of contrast light trigger.

the typical curve of table 3 light trigger and detectability

2. the repeatability of method and recovery of standard addition:

The standard solution II (concentration is 1 μ g/mL) of the standard solution I (concentration is 100 μ g/mL) of the light trigger of 10 μ L, 50 μ L and 200 μ L and the light trigger of 10 μ L, 50 μ L and 200 μ L is added respectively in blank MPPO, carry out pre-treatment and LC-MS/MS analysis respectively, and calculate its recovery according to adding scalar sum measured value, the results are shown in Table 4.As can be seen from Table 4, the average recovery rate of light trigger is between 77.4% ~ 115.4%, and average relative standard's deviation (RSD), between 1.5% ~ 8.1%, illustrates that the recovery of the inventive method is high, reproducible.

the recovery of table 4 light trigger and repeatability (n=5)

Example 2:

Traditional C 18 post and fluorophenyl chromatographic column has been investigated to the difference of 15 kinds of light trigger separation case in this example.Due to investigated 15 kinds of light triggers, there is similar, be difficult to the feature of separation, good compartment analysis effect can not be reached by traditional C18 chromatographic column, and it is bad to have peak type, affects the shortcoming of quantitative result.And the Luna PFP (2) selected (150 mm × 4.6 mm, 3 μm) chromatographic column, be connected with propyl group by pentafluorophenyl group, for high polarity, complicated natural products and isomeride etc. provide significant selectivity.It provide the multiple retention mechanism different from other reversed material, be very suitable for halo, fragrance and conjugated compound.Use Luna PFP (2) post to be separated 15 kinds of light triggers, can not only have good separating effect, and peak type is better, sensitivity is also higher, and LC-MS/MS chromatogram is shown in Fig. 2.

Example 3:

As can be seen from example 1, the limitation due to involved light trigger is minimum is 0.01 mg/kg, meets the sensitivity requirement of the method completely, and therefore pretreatment process can adopt 4 g MPPO in 1 g MPPO replacement EU criteria.Because MPPO is expensive and recycling process is loaded down with trivial details, reduce the use amount of MPPO in pretreatment process and also under the prerequisite meeting sensitivity requirement, reduce cost.This example compare migration experiment pack sample area and Noryl analogies mass ratio be respectively 1dm ²: 4g and 0.25dm ²: the migration amount of 1g two kinds of situations, experimental result is in table 5, as can be seen from experimental result, two kinds of migration trial scale comparisons do not have significant difference, utilize this method can adopt migration experiment pack sample area and Noryl analogies mass ratio be respectively 0.25dm ²: 1g.The advantage of this process under the procedure condition meeting foreign laws laws and regulations requirement, can greatly reduce testing cost.

the comparison of the testing result of two kinds, table 5 migration experimentation migration amount

Example 4:

As described in Example 1, select Product Quality Verification Centers homemade UV ink color development sample, record the Special migration of light trigger in sample in table 6.

the testing result of light trigger Special migration in table 6 sample

Sequence number	Title is abridged	Light trigger Special migration (mg/kg) in sample
			1	1173	8.60
2	BP	103.00
			3	2-MBP	259.20
4	EDB	68.80
			5	BDK	31.70
6	OMBB	44.60
			7	EHDBA	63.10
8	Irgacure 907	1.44
			9	2-ITX	9.04
10	PBZ	23.50
			11	DETX	7.51
12	MK	0.01
			13	DEAB	0.01
14	Irgacure 369	—
			15	Irgacure 2959	—

Note: "-" represents and do not detect

list of references

[1] Binderup M L, Pedersen G A, Vinggaard A, Rasmussen E, Rosenquist H,Cederberg T, Food. Addit. Contam., 2002. 19(S1): 13-28.

[2] HAN Wei, YU Yan-Jun, LI Ning-Tao, WANG Li-Bing. Chinese J. Anal. Chem., 2011, 39(9): 1387-1393.

Han Wei, Yu Yanjun, Li Ningtao, Wang Libing, analytical chemistry, 2011,39 (9): 1387-1393

[3] Opinion of the scientific panel of food additives, flavourings, processing aids and materials in contact with food on a request from the commission related to 2-isopropyl thioxanthone (ITX) and 2-ethylhexyl-4-dimethylamino benzoate (EHDAB) in food contact materials, EFSA J. 293 (2005) 1 (available at http://www.efsa.eu.int/science /afc/afc opinions/catindex en.html).

[4] Ordinance of the FDHA on articles and materials (RS 817.023.21) of 23 November 2005 (available at http://www. admin.ch/ch/f/rs/c817_023_21.html).

[5] Policy statement concerning paper and board materials and articles intended to come into contact with foodstuffs of 02 December 2009 (available at http://www.coe.int/t/e/ social_cohesion/soc-sp/ public_health/ food_contact/).

[6] European Commission Health and Consumers Directorate-General. Standing Committee on the Food Chain and Animal Health Section Toxicological Safety Conclusions of the meeting of 06 March 2009 (available at http:// www.food.gov.uk/science/surveillance/fsisbranch2006/ fsis1806).

[7] EuPIA Suitability List of Photo-initiators for Low Migration UV Printing Inks and Varnishes of June 2010 (available at http://www.eupia.org).

[8] ResAP (2002) 1 resolves about paper and paperboard material and the goods of intending Food Contact.

[9] Sagratini G, Caprioli G, Cristalli G, Giardiná D, Ricciutelli M, Volpini R, Zuo Y,Vittori S, J. Chromatogr. A., 2008. 1194(2): 213-220

[10] Morlock G,Schwack W, Anal. Bioanal. Chem., 2006. 385(3): 586-595.

[11] Benetti C, Angeletti R, Binato G, Biancardi A,Biancotto G, Anal. Chim. Acta., 2008. 617(1): 132-138.

[12] Sanches-Silva A, Pastorelli S, Cruz J, Simoneau C, Castanheira I,Paseiro-Losada P, J.Dairy. Sci., 2008. 91(3): 900-909。

Claims (5)

1. one kind based on light trigger in LC-MS/MS technical Analysis printed wrapper to the method for MPPO migration amount, it is characterized in that: be that the light trigger object that discharges under simulated conditions of a kind of sample is after Noryl MPPO adsorbs, with acetonitrile, solvent extraction is carried out to MPPO, filter the method measuring light trigger Special migration in printed apcksging material with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) after supernatant concentration, concrete steps are as follows:

A, preparation of samples: take about MPPO, evenly tiling is to moving apparatus, will be laid in above MPPO after the cutting of wrapping paper sample, pending migration experiment after sealing moving apparatus;

B, migration experiment: moving apparatus is carried out heating and carry out migration experiment, take out and be cooled to room temperature;

C, oscillation extraction: transferred to by the MPPO in moving apparatus in tool plug centrifuge tube, add the acetonitrile of certain volume, with speed vortex oscillation 10 min of 2000 r/min on vortex oscillation instrument, then with centrifugal 5 min of 8000 r/min;

D, concentrated: the extract getting 1-4 mL is placed on Nitrogen evaporator and is concentrated into 1mL, after 0.22 μm of organic phase membrane filtration, carry out LC-MS/MS analysis;

The configuration of e, extraction standard working solution: take the various light trigger sterling of 0.05 g respectively, be accurate to 0.1 mg, be placed in 10 mL volumetric flasks, dissolves and constant volume with acetonitrile, is mixed with the single standard solution that concentration is 5 mg/mL; Then be made into the acetonitrile solution of mixed standard solution, and be finally mixed with the standard working solution of the various light triggers of the pure acetontrile with concentration gradient; Take blank MPPO, repeat c, Step d, after concentrated for extract drying up, then redissolve with the standard working solution of pure acetontrile at different levels, be finally mixed with the extraction standard working solution of the various light triggers with same concentration gradient;

F, LC-MS/MS measure: the extraction standard working solution drawing the variable concentrations prepared, and after crossing 0.22 μm of organic filter membrane, inject LC-MS/MS and analyze;

When LC-MS/MS measures, the liquid phase chromatogram condition of employing is: chromatographic column: Luna PFP (2): 150 mm × 4.6 mm, 3 μm; Mobile phase: acetonitrile/0.1% aqueous formic acid, flow velocity: 500 μ L/min; Gradient elution; Column temperature: 30 DEG C; Sample size: 10 μ L; The Mass Spectrometry Conditions adopted: scan mode: positive ion scans; Electric spray ion source (ESI); Atomization gas flow is 50 psi; Gas curtain airshed 15 psi; Auxiliary heating airshed is 50 psi; Ionization temperature 500 DEG C; Impinging air flows amount is 10 psi; 4 kinds of gases are nitrogen; The residence time is 50 msec; Ionization voltage 5500 V, detection mode: positive ion polyion reaction monitoring (MRM);

Gradient elution program sees the following form:

liquid chromatogram mobile phase composition, flow velocity and graded

The calculating of h, result: join with matrix the quantitative test that mark external standard method carries out light trigger object, namely with the secondary Selective ion mode peak area of light trigger, regretional analysis is carried out to its respective concentration, obtain typical curve; Sample after extracting is measured, records the secondary Selective ion mode peak area of light trigger, substitute into typical curve, try to achieve the Special migration of light trigger in sample; Final migration amount result is with the migration amount of unit area packaging light trigger and mg/dm ²or the content mg/kg of light trigger counts in unit mass Noryl.

2. according to claim 1ly, to it is characterized in that to the method for MPPO migration amount based on light trigger in LC-MS/MS technical Analysis printed wrapper: Noryl MPPO and the input ratio of wrapping paper sample are the corresponding 0.25dm of 1g Noryl MPPO ²wrapping paper sample area.

3. according to claim 1ly, to it is characterized in that to the method for MPPO migration amount based on light trigger in LC-MS/MS technical Analysis printed wrapper: described moving apparatus is tool lid double dish or tool plug measuring cup that can be airtight.

4. according to claim 1ly, to it is characterized in that to the method for MPPO migration amount based on light trigger in LC-MS/MS technical Analysis printed wrapper: the ratio 10mL:1g of acetonitrile solvent volume used and Noryl quality during extraction.

5. according to claim 1 based on light trigger in LC-MS/MS technical Analysis printed wrapper to the method for MPPO migration amount, it is characterized in that: the manner of formulation of extraction standard working solution is as follows: take the various light trigger sterling of 0.05 g respectively, be accurate to 0.1 mg, be placed in 10 mL volumetric flasks, dissolve and constant volume with acetonitrile, be mixed with the list mark that concentration is 5 mg/mL; Respectively often kind of single standard is really pipetted 1 mL, be placed in 50mL volumetric flask, with acetonitrile constant volume, be mixed with the mixed standard solution I that each target concentration is 100 μ g/mL; Then accurately pipette 1 mL mixed standard solution I, be placed in 10 mL volumetric flasks, use acetonitrile constant volume, be mixed with the mixed standard solution II that each target concentration is 1 μ g/mL;

The preparation of extraction standard solution I: the mixed standard solution I accurately pipetting 0.01 mL, 0.02 mL, 0.05 mL, 0.10 mL and 0.20 mL, with acetonitrile constant volume in 10 mL, obtains the series standard working solution of neat solvent preparation; Take blank MPPO, repeat c, Step d, after concentrated for 1mL extract drying up, then redissolve with the standard working solution of the pure acetontrile of 1mL, matrix series standard solution I concentration of final preparation is: 100 ng/mL, 200 ng/mL, 500 ng/mL, 1000 ng/mL, 2000 ng/mL;

The preparation of extraction standard solution II: the mixed standard solution II accurately pipetting 0.01 mL, 0.02 mL, 0.05 mL, 0.10 mL and 0.20 mL, with acetonitrile constant volume in 2.5 mL, obtains the series standard working solution of neat solvent preparation.Take blank MPPO, repeat c, Step d, after concentrated for 4 mL extracts drying up, redissolve with the standard working solution of the pure acetontrile of 1mL, matrix series standard solution II concentration of final preparation is: 4 ng/mL, 8 ng/mL, 20 ng/mL, 40 ng/mL, 80 ng/mL, 200 ng/mL again.