A quality detection method for volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials

Abstract

The present invention provides a quality detection method for volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials, comprising the following steps: preparing a double internal standard solution; sample detection. The present invention uses two deuterated substances with large boiling point differences as internal standards for the first time to correct the chromatograms of volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials. The present invention adds two deuterated substances to effectively correct the chromatograms of volatile and semi-volatile substances between parallel samples detected, and significantly improves the spectral repeatability between parallel samples. The present invention adds two deuterated substances to effectively correct the retention time change offset caused by replacing the chromatographic column, turning the instrument on and off, and different detection periods.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical composition detection of packaging materials, and relates to a quality detection method for volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials, and specifically relates to a method for detecting volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials and correcting chromatograms by using deuterated benzene and deuterated naphthalene double internal standards combined with headspace gas chromatography. Background Art

[0002] In the production process of paper packaging and printing, volatile and semi-volatile organic compounds in raw and auxiliary materials such as paper, ink, solvent and glue may remain in the printed products. For packaging and printing, the residual volatile and semi-volatile organic compounds may affect the smell of the material itself; for packaged food, the residual volatile and semi-volatile components in packaging and printing may migrate into the food, thereby affecting the quality of the food. At present, the control of volatile and semi-volatile organic compounds in paper packaging and printing and raw and auxiliary materials is mainly based on the quantitative detection and judgment of limit indicators and the quantitative or semi-quantitative detection of corresponding compounds. However, within the range of limit indicators meeting the requirements, the large fluctuations in the content of volatile and semi-volatile organic compounds such as propylene glycol methyl ether and benzene series in the used solvents may bring about changes in the sensory smell of the material itself; some residual substances such as butyl acrylate, isooctyl acrylate, sesquiterpenes, etc. may migrate into food and bring about changes in food flavor quality. In the production process of paper packaging printed materials and raw and auxiliary materials, changes in factors such as process improvements, raw material batch differences and placement time may affect the content of volatile and semi-volatile organic compounds in printed products, and the existing control methods do not consider the possible impact of the volatility of such substances. Therefore, it is necessary to establish a consistency evaluation technology for volatile and semi-volatile components in packaging printed materials and raw and auxiliary materials to evaluate their volatility. Among them, the detection of such substances in printed materials and raw and auxiliary materials and the correction of characteristic spectra are crucial for consistency evaluation.

[0003] In order to further improve the quality stability of packaging printed materials and raw and auxiliary materials, it is necessary to establish the detection of volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials and the correction of specific spectra to provide technical support for the quality stability evaluation of printed materials and raw materials. At present, among the detection methods of volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials at home and abroad, there is no report on the detection of volatile substances in packaging printed materials and raw and auxiliary materials and the correction of chromatograms based on double internal standards of deuterated benzene and deuterated naphthalene combined with gas chromatography. Summary of the invention

[0004] In view of the shortcomings of the prior art described above, the object of the present invention is to provide a quality detection method for volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials, so as to solve the problem in the prior art of lack of effective correction of chromatograms of volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials.

[0005] To achieve the above-mentioned and other related purposes, the present invention provides a method for quality detection of volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials, comprising the following steps:

[0006] 1) Preparation of double internal standard solution: adding two deuterated compounds to a solvent to make a double internal standard solution;

[0007] 2) Sample testing: Add the double internal standard solution of step 1) to a series of paper packaging printed materials or raw and auxiliary materials as test samples, and analyze them by headspace-gas chromatography-mass spectrometry. Compare the retention time of the analyte and the internal standard of each test sample in a series of chromatograms with the average retention time of the internal standard in the series of chromatograms, calculate and obtain the corrected retention time of a series of test samples, and then calculate the correlation coefficient between a series of corrected chromatograms through the corrected retention time, construct the quality control interval in the cigarette packaging material, and conduct consistency evaluation on subsequent test samples.

[0008] When comparing the reference response value corresponding to the reference correction retention time with the response values ​​corresponding to the correction retention times of other samples to be tested, the response values ​​corresponding to all retention times in the chromatogram are compared.

[0009] Preferably, in step 2), the printing raw and auxiliary materials are selected from one or more of paper, ink, varnish, adhesive and electroplated aluminum.

[0010] The packaging printed product comprises substrate paper, ink, varnish, adhesive and electrochemical aluminum.

[0011] The series of paper packaging printed materials or raw and auxiliary materials are paper packaging printed materials or raw and auxiliary materials from different periods and batches.

[0012] Preferably, in step 1), the boiling point difference between the two deuterated compounds exceeds 100°C.

[0013] Preferably, in step 1), the two deuterated compounds are deuterated benzene and deuterated naphthalene.

[0014] Preferably, in step 1), the solvent is a compound that does not interfere with the detection of volatile and semi-volatile substances.

[0015] Preferably, in step 1), the internal standard concentration in the double internal standard solution is 0.05-0.5 mg / mL.

[0016] Preferably, in step 15), one of the two deuterated compounds has a boiling point of 60-90°C and the other has a boiling point of 200-240°C;

[0017] Preferably, in step 1), the solvent is triacetin or N,N-dimethylformamide.

[0018] Preferably, in step 1), the internal standard concentration in the double internal standard solution is 0.1-0.3 mg / mL.

[0019] Preferably, in step 2), the area of ​​the paper packaging printed matter, paper and anodized aluminum is 50-160 cm 2 .

[0020] More preferably, in step 2), the area of ​​the paper packaging printed matter and the paper is 110-160 cm 2 , the area of ​​anodized aluminum is 50-60cm 2 ;

[0021] Preferably, in step 2), the amount of ink and varnish used is 0.05-0.15 g, and the amount of adhesive used is 0.4-1 g.

[0022] Preferably, in step 2), the volume of the double internal standard solution added is 20-60 μL.

[0023] More preferably, in step 2), when preparing the paper packaging printed matter, paper, anodized aluminum and adhesive test samples, the added volume of the double internal standard solution is 20-40 μL;

[0024] More preferably, in step 3), when the ink sample to be tested is prepared, when the main solvent in the ink is water, the added volume of the double internal standard solution is 20-40 μL;

[0025] More preferably, in step 3), when the ink sample to be tested is prepared, when the main solvent in the ink is an organic solvent, the added volume of the double internal standard solution is 40-60 μL.

[0026] Preferably, the headspace conditions are: equilibrium temperature: 80-120°C, equilibrium time: 30-60min;

[0027] The chromatographic conditions are:

[0028] Chromatographic column: Supelco VOC special capillary column, specifications are [60m (length) × 0.32mm (inner diameter) × 1.8μm (film thickness)];

[0029] Inlet temperature: 200-250℃;

[0030] Carrier gas: Helium purity ≥99.999%, constant flow mode, flow rate 1-3mL / min;

[0031] Inlet split ratio: (1-60): 1;

[0032] Heating program: 40℃-50℃, hold for 2min-4min, increase the temperature to 190℃-220℃ at a rate of 4℃ / min-10℃ / min, hold for 10min-15min.

[0033] The mass spectrometry conditions were as follows: ion source temperature: 200-250°C; quadrupole temperature: 150°C; measurement method: full scan mode; scan range: 29-350 amu.

[0034] Preferably, in step 2), when testing paper packaging printed materials, paper, electroplated aluminum and adhesive samples, the inlet split ratio is (1-4):1.

[0035] Preferably, in step 2), when the ink sample is tested, when the main solvent in the ink is water, the split ratio of the injection port is (1-4):1.

[0036] Preferably, in step 2), when the ink sample is tested, when the main solvent in the ink is an organic solvent, the split ratio of the injection port is (50-60):1.

[0037] Preferably, in step 2), the calculation formula of the corrected retention time of the sample to be tested includes the following:

[0038] When R t <R t内标1 When , calculate according to formula (1):

[0039] The formula (1):

[0040] In formula (1), R t1 Corrected retention time for the analyte, R t is the retention time of the analyte, R t内标1 is the retention time of internal standard 1 in the sample, is the average retention time of internal standard 1 in multiple samples.

[0041] When R t内标1 <R t <R t内标2 When , calculate according to formula (2):

[0042] The formula (2):

[0043] In formula (2), R t1 Corrected retention time for the analyte, R tis the retention time of the analyte, R t内标1 is the retention time of internal standard 1 in the sample, is the average retention time of internal standard 1 in multiple samples, R t内标2 is the retention time of internal standard 2 in the sample, is the average retention time of internal standard 2 in multiple samples.

[0044] When R t >R t内标2 When , calculate according to formula (3):

[0045] The formula (3):

[0046] In formula (3), R t1 Corrected retention time for the analyte, R t is the retention time of the analyte, R t内标2 is the retention time of internal standard 2 in the sample, is the average retention time of internal standard 2 in multiple samples;

[0047] The internal standard 1 is deuterated benzene and the internal standard 2 is deuterated naphthalene.

[0048] Preferably, in step 2), the calculation of the correlation coefficient between a series of corrected chromatograms by corrected retention time comprises: setting the corrected retention time of a sample to be tested in a series of samples to be tested as the reference corrected retention time, and then comparing the reference response value corresponding to the reference corrected retention time with the response values ​​corresponding to the corrected retention times of other samples to be tested, and calculating the correlation coefficient between the series of corrected chromatograms according to formula (4),

[0049] Formula (4) is:

[0050] Formula (4): r is the correlation coefficient between spectrum a and spectrum b, a i is the response value at the i-th retention time in the spectrum a, a is the average value of the spectrum response, b i is the response value at the i-th retention time in spectrum b, is the average response value of spectrum b, and n is the retention time sequence number in the spectrum.

[0051] Preferably, in step 2), constructing the quality control interval in the cigarette packaging material includes: calculating the relative standard deviation of the correlation coefficient between a series of calibrated chromatograms, and constructing the quality control interval with 2 times the standard deviation (2 STD, confidence level 95.5%) or 3 times the standard deviation (3 STD, confidence level 99.7%) as the limit.

[0052] Preferably, in step 2), the consistency evaluation refers to that the correlation coefficient between the calibrated chromatograms of subsequent paper packaging printed materials or raw and auxiliary materials calculated by the above method is regarded as conforming to the consistency within the quality control interval, and is regarded as not conforming to the consistency beyond the quality control interval.

[0053] As described above, the present invention has the following beneficial effects:

[0054] 1) The present invention proposes for the first time a method for detecting and spectrally correcting volatile and semi-volatile substances in printing raw and auxiliary materials including ink, anodized aluminum and adhesive.

[0055] 2) The present invention is the first to use two deuterated substances with large boiling point differences as internal standards to calibrate the chromatograms of volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials.

[0056] 3) The present invention adds two deuterated substances to effectively correct the chromatograms of volatile and semi-volatile substances between the detected parallel samples, and significantly improve the spectral repeatability between the parallel samples.

[0057] 4) The present invention adds two deuterated substances to effectively correct the retention time variation caused by replacing the chromatographic column, turning the instrument on and off, and different detection periods. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 Shown is the quality control chart of Example 2 of the present invention.

[0059] Figure 2 Shown is a dendrogram of the comparative example of the present invention, wherein,

[0060] In Figure A:

[0061] 1: Correlation coefficient between parallel samples of paper packaging printed materials - the spectrum was not corrected with internal standard;

[0062] 2: Correlation coefficient between parallel samples of paper packaging printed materials - spectrum single internal standard (deuterated benzene) correction;

[0063] 3: Correlation coefficient between parallel samples of paper packaging printed materials - spectrum double internal standard (deuterated benzene, deuterated naphthalene) correction;

[0064] In Figure B:

[0065] 4: Correlation coefficient between parallel samples before and after 2 months - the spectra were not corrected with internal standards;

[0066] 5: Correlation coefficient between parallel samples before and after 2 months - spectrum single internal standard (deuterated benzene) calibration;

[0067] 6: Correlation coefficient between parallel samples before and after 2 months - spectrum double internal standard (deuterated benzene, deuterated naphthalene) calibration.

[0068] Figure 3 Shown is a chromatogram of a comparative example of the present invention, wherein,

[0069] In Figure A:

[0070] 1: Spectrum of sample collected 2 months ago - the spectrum was not corrected with internal standard;

[0071] 2: Spectrum collected after 2 months - the spectrum was not corrected with internal standard;

[0072] In Figure B:

[0073] 3: Spectrum of sample collected 2 months ago - spectrum calibration with double internal standards (deuterated benzene and deuterated naphthalene);

[0074] 4: Sample collection spectrum 2 months later - spectrum double internal standard (deuterated benzene, deuterated naphthalene) calibration. DETAILED DESCRIPTION

[0075] The present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention.

[0076] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0077] The reagents and experimental tools used in the following examples are all commonly used reagents and experimental tools, and can be purchased from the market.

[0078] Example 1

[0079] 1. Preparation of internal standard solution

[0080] Weigh 20 mg of deuterated benzene (CAS No.: 1076-43-3) and deuterated naphthalene (CAS No.: 1146-65-2) standard substances into a 100 mL volumetric flask, and dilute to volume with triacetin to obtain a mixed internal standard solution with a concentration of 0.20 mg / mL.

[0081] 2. Sample preparation

[0082] 2.1 Paper packaging printed materials or paper

[0083] Take a paper packaging print or paper sample and cut out an area of ​​121cm 2 The sample should include the main packaging surface. Roll the cut sample into a tube with the printed surface facing inwards. Immediately put it into a headspace bottle. Add 30μL of internal standard solution and seal it for testing.

[0084] 2.2 Ink

[0085] Weigh 0.1g of ink (the solvent is mainly water-based) and put it into a headspace bottle, add 30μL of internal standard solution, seal it and wait for testing; weigh 0.1g of ink (the solvent is mainly organic solvent) and put it into a headspace bottle, add 60μL of internal standard solution, seal it and wait for testing.

[0086] 2.3 Adhesive

[0087] Weigh 0.5 g of glue into a headspace bottle, add 30 μL of internal standard solution, seal and wait for testing.

[0088] 2.4 Anodized Aluminum

[0089] Cut 54cm 2 The electrochemical aluminum was placed in a headspace bottle, 30 μL of internal standard solution was added, and the bottle was sealed for testing.

[0090] 2.5 Varnish

[0091] Weigh 0.1 g of varnish into a headspace bottle, add 30 μL of internal standard solution, seal and wait for testing.

[0092] 3. Gas chromatography conditions

[0093] Chromatographic column: Supelco VOC special capillary column, specification is [60m (length) × 0.32mm (inner diameter) × 1.8μm (film thickness)].

[0094] Inlet temperature: 220℃.

[0095] Carrier gas: Helium purity ≥ 99.999%, constant flow mode, flow rate 2 mL / min.

[0096] Split ratio: 1:1 (testing of paper packaging printing materials, paper, water-based ink, varnish, anodized aluminum and adhesive); Split ratio: 50:1 (testing of solvent-based gravure ink).

[0097] Heating program: 40°C, hold for 2 min, increase to 200°C at a rate of 4°C / min, hold for 10 min.

[0098] Example 2

[0099] On different days of delivery, a total of 9 batches of gravure ink samples were tested. 0.1g of ink was taken and placed in a headspace bottle. 60μL of internal standard solution was added. The samples were tested by headspace-gas chromatography / mass spectrometer. The chromatograms were collected and the correlation coefficients between the spectra were calculated after correction with double internal standards. The correlation coefficients of the last 8 batches of samples and the first batch of samples were calculated based on the first batch of samples to monitor the volatility of volatile and semi-volatile substances in the samples. The results showed that the correlation coefficient ranged from 0.9801 to 0.9972. The quality stability of this indicator in different batches of ink was good. The quality control chart is shown in Figure 1 , the correlation coefficient between the two chromatograms is calculated using formula (4). The closer the correlation coefficient is to 1, the stronger the correlation is, indicating that the difference between the two chromatograms is smaller.

[0100]

[0101] Where: r is the correlation coefficient between spectrum a and spectrum b, a i is the response value at the i-th retention time in the spectrum a, a is the average value of the spectrum response, b i is the response value at the i-th retention time in spectrum b, is the average response value of spectrum b, and n is the retention time sequence number in the spectrum.

[0102] Comparative Example 1-1

[0103] Taking 5 parallel typical paper packaging printed materials as samples, samples with an area of ​​22.0 cm × 5.5 cm were cut. The samples included the main packaging surface. The printed surface of the cut samples was rolled into a tube inward and immediately placed in a headspace bottle. The samples were tested by headspace-gas chromatography / mass spectrometry. The chromatograms were collected and the correlation coefficients between the spectra of the 5 samples were calculated. The results are shown in Table 1. The minimum correlation coefficient was 0.9088.

[0104] Table 1 Correlation coefficients between spectra of 5 parallel samples

[0105]

[0106] Comparative Example 1-2

[0107] On the basis of Comparative Example 1, 30 μL of deuterated benzene internal standard was added to the headspace bottle, chromatograms were collected and correlation coefficients between the spectra of 5 samples were calculated. The results are shown in Table 2. The minimum correlation coefficient was 0.9396.

[0108] Table 2 Correlation coefficients between spectra of 5 parallel samples

[0109]

[0110] Comparative Examples 1-3

[0111] On the basis of Comparative Example 1, 30 μL of deuterated benzene and 30 μL of deuterated naphthalene internal standard were added to the headspace bottle, chromatograms were collected and the correlation coefficients between the spectra of 5 samples were calculated. The results are shown in Table 3. The minimum correlation coefficient is 0.9824.

[0112] Table 3 Correlation coefficients between spectra of 5 parallel samples

[0113]

[0114] The comprehensive results of Comparative Examples 1-1, 1-2 and 1-3 are shown in the attached Figure 2 A. As can be seen from the figure, compared with before calibration, the correlation coefficient between spectra is improved after calibration with single internal standard deuterated benzene. After calibration with double internal standard deuterated benzene and deuterated naphthalene, the correlation coefficient between spectra is significantly improved, and the minimum correlation coefficient reaches 0.9824, indicating that double internal standard calibration can significantly improve the spectral repeatability between parallel samples.

[0115] Comparative Example 2-1

[0116] Two groups of identical paper packaging printed samples were prepared, each group containing 5 parallel samples. For each of the samples in one group, a sample with an area of ​​22.0 cm × 5.5 cm was cut, and the sample contained the main packaging surface. The printed surface of the cut sample was rolled into a cylinder, and immediately placed in a headspace bottle, and tested with a headspace-gas chromatography / mass spectrometer to collect chromatograms. After an interval of 2 months, the instrument was turned off and on and the chromatographic column was replaced. The other group of samples was prepared in the same way and the chromatogram was collected. The correlation coefficient of the spectra between the two groups of samples was calculated. The results are shown in Table 4. The minimum correlation coefficient is 0.4076.

[0117] Table 4 Correlation coefficients between spectra of two groups of samples

[0118]

[0119] Comparative Example 2-2

[0120] On the basis of Comparative Example 2-1, 30 μL of deuterated benzene internal standard was added to the headspace bottle, chromatograms were collected and the correlation coefficients between the two groups of samples were calculated. The results are shown in Table 5. The minimum correlation coefficient was 0.9363.

[0121] Table 5 Correlation coefficients between spectra of two groups of samples

[0122]

[0123] Comparative Examples 2-3

[0124] On the basis of Comparative Example 2-1, 30 μL of deuterated benzene and 30 μL of deuterated naphthalene internal standard were added to the headspace bottle, chromatograms were collected and the correlation coefficients between the two groups of samples were calculated. The results are shown in Table 6. The minimum correlation coefficient was 0.9629.

[0125] Table 6 Correlation coefficients between spectra of two groups of samples

[0126]

[0127] The comprehensive results of Comparative Examples 2-1, 2-2 and 2-3 are shown in the attached Figure 2 B, chromatogram see Figure 3 . As can be seen from the figure, before correction, the minimum correlation coefficient between spectra was 0.4076, because the peak retention time changed significantly after the chromatographic column was replaced. After correction by single internal standard method, the correlation coefficient between spectra was significantly improved. After correction by double internal standard method, the correlation coefficient between spectra was further improved, and the minimum correlation coefficient reached 0.9629, indicating that the double internal standard method correction can correct the retention time offset caused by instrument power on and off and replacement of chromatographic columns, and significantly improve the spectral repeatability of samples between groups.

[0128] Therefore, the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.

[0129] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A quality detection method for volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials, comprising the following steps: 1) preparing a double internal standard solution: adding two deuterated compounds to a solvent to make a double internal standard solution; the difference in boiling points of the two deuterated compounds is greater than 100° C.; the two deuterated compounds are deuterated benzene and deuterated naphthalene; 2) Sample testing: Add the double internal standard solution of step 1) to a series of paper packaging printed materials or raw and auxiliary materials as test samples, and analyze them by headspace-gas chromatography-mass spectrometry. Compare the retention time of the analyte and the internal standard of each test sample in a series of chromatograms with the average retention time of the internal standard in the series of chromatograms, calculate and obtain the corrected retention time of a series of test samples, and then calculate the correlation coefficient between a series of corrected chromatograms through the corrected retention time, construct the quality control interval in the cigarette packaging material, and conduct consistency evaluation on subsequent test samples.

2. The quality detection method for volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials according to claim 1, characterized in that: In step 2), the raw and auxiliary materials are selected from one or more of paper, ink, varnish, adhesive or electroplated aluminum.

3. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 1, characterized in that: Include at least one of the following technical features: 13) In step 1), the solvent is a compound that does not interfere with the detection of volatile and semi-volatile substances; 14) In step 1), the internal standard concentration in the double internal standard solution is 0.05-0.5 mg / mL.

4. The quality detection method of volatile and semi-volatile substances in packaging printed materials and raw and auxiliary materials according to claim 1, characterized in that: In step 1), the solvent is triacetin or N,N-dimethylformamide; And / or the two deuterated compounds, one of which has a boiling point of 60-90°C and the other of which has a boiling point of 200-240°C.

5. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 1, characterized in that: In step 1), the internal standard concentration in the double internal standard standard solution is 0.1-0.3 mg / mL.

6. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 2, characterized in that: Include at least one of the following technical features: 21) In step 2), the area of ​​paper packaging printed matter, paper and anodized aluminum is 50-160cm 2 ; 22) In step 2), the amount of ink and varnish is 0.05-0.15g, and the amount of adhesive is 0.4-1g; 23) In step 2), the volume of the double internal standard solution added is 20-60 μL.

7. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 2, characterized in that: In step 2), the headspace conditions are: equilibrium temperature: 80-120°C, equilibrium time: 30-60min; The chromatographic conditions are: 31) Chromatographic column: Supelco VOC special capillary column, specification is 60m×0.32mm×1.8μm, length×inner diameter×film thickness; 32) Inlet temperature: 200-250°C; 33) Carrier gas: Helium purity ≥ 99.999%, constant flow mode, flow rate 1-3 mL / min; 34) Inlet split ratio: (1-60): 1; 35) Heating program: 40°C-50°C, hold for 2 min-4 min, increase the temperature to 190°C-220°C at a rate of 4°C / min-10°C / min, hold for 10 min-15 min; The mass spectrometry conditions were as follows: ion source temperature: 200-250°C; quadrupole temperature: 150°C; measurement method: full scan mode; scan range: 29-350 amu.

8. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 1, characterized in that: Include at least one or more of the following technical features: 41) In step 2), when testing paper packaging printed matter, paper, anodized aluminum and adhesive samples, the inlet split ratio is (1-4): 1; 42) In step 2), when the ink sample is tested, when the main solvent in the ink is water, the split ratio of the injection port is (1-4): 1; 43) In step 2), when the ink sample is tested, when the main solvent in the ink is an organic solvent, the inlet split ratio is (50-60):

1.

9. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 1, characterized in that: In step 2), the calculation formula of the corrected retention time of the sample to be tested includes the following: When R t <R t内标1 When , calculate according to formula (1): The formula (1): In formula (1), R t1 Corrected retention time for the analyte, R t is the retention time of the analyte, R t内标1 is the retention time of internal standard 1 in the sample, is the average retention time of internal standard 1 in multiple samples; When R t内标1 <R t <R t内标2 When , calculate according to formula (2): The formula (2): In formula (2), R t1 Corrected retention time for the analyte, R t is the retention time of the analyte, R t内标1 is the retention time of internal standard 1 in the sample, is the average retention time of internal standard 1 in multiple samples, R t内标2 is the retention time of internal standard 2 in the sample, is the average retention time of internal standard 2 in multiple samples; When R t >R t When the internal standard is 2, calculate according to formula (3): The formula (3): In formula (3), R t1 Corrected retention time for the analyte, R t is the retention time of the analyte, R t内标2 is the retention time of internal standard 2 in the sample, is the average retention time of internal standard 2 in multiple samples; The internal standard 1 is deuterated benzene and the internal standard 2 is deuterated naphthalene.

10. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 1, characterized in that: In step 2), the correlation coefficients between a series of calibrated chromatograms are calculated by correcting the retention time, including: setting the corrected retention time of a sample to be tested in a series of samples to be tested as the reference corrected retention time, and then comparing the reference response value corresponding to the reference corrected retention time with the response values ​​corresponding to the corrected retention times of other samples to be tested, and calculating the correlation coefficients between the series of calibrated chromatograms according to formula (4), The formula (4) is: Formula (4): r is the correlation coefficient between spectrum a and spectrum b, a i is the response value at the i-th retention time in the spectrum a, a is the average value of the spectrum response, b i is the response value at the i-th retention time in spectrum b, is the average response value of spectrum b, and n is the retention time sequence number in the spectrum.

11. The quality detection method of volatile and semi-volatile substances in packaging printed matter and raw and auxiliary materials according to claim 1, characterized in that: In step 2), the construction of the quality control interval in the cigarette packaging material includes: calculating the relative standard deviation of the correlation coefficient between a series of calibrated chromatograms, and constructing the quality control interval with the average retention time and the standard deviation as the limit.

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