A method for determining volatile substances in paper outer packaging material auxiliaries

Abstract

The application relates to the technical field of paper outer packaging material auxiliary material detection, in particular to a method for determining volatile substances in paper outer packaging material auxiliary materials, which comprises the following steps: (1) taking paper outer packaging material auxiliary material samples, using a headspace sampling mode to send the volatile substances in the samples into a gas chromatography-mass spectrometer for non-target detection, and performing qualitative and quantitative analysis on the volatile substances in the samples; (2) according to the time sequence, using an olfactory method to perform sensory evaluation on the volatile substances of the samples and establishing a sample quality discrimination model, inputting the sensory evaluation results into the sample quality discrimination model to calculate the stimulating odor dissipation score of the samples, and analyzing the irritancy of the volatile substances of the samples according to the stimulating odor dissipation score of the samples. The application can accurately and effectively detect the volatile substances of various different kinds of paper outer packaging material auxiliary materials.

Description

Technical Field

[0001] This application relates to the field of paper packaging material auxiliary material testing technology, and in particular to a method for determining volatile substances in paper packaging material adhesives. Background Technology

[0002] The processing of paper packaging materials for alcoholic beverages involves various types of auxiliary materials, such as water-based laminating adhesives, gift box adhesives, mounting adhesives, sealing adhesives, hot melt adhesives, fine mounting adhesives, and water-based white glue. These adhesives are applied to paper packaging materials such as labels, boxes, bags, and cartons according to production needs. Large-scale wineries package tens of thousands of tons of wine annually, requiring a large amount of paper packaging materials. However, the quality of auxiliary materials used in alcoholic beverage paper packaging varies greatly. If these materials emit a noticeable odor, it will negatively impact the product image and consumer experience. Therefore, it is essential to test for volatile substances in the auxiliary materials used in alcoholic beverage paper packaging materials and monitor their quality.

[0003] Currently, existing technologies include solid-phase microextraction combined with gas chromatography-mass spectrometry (GC-MS) for detecting volatile substances in adhesives used in food-grade cigarette packaging materials. This method detects several specific organic substances in the packaging material auxiliary materials, using standard solutions for quantitative analysis. However, this method cannot provide a comprehensive analysis of volatile substances in packaging material auxiliary material samples. Furthermore, relying solely on instrumental analysis is limited and cannot effectively assess the quality of packaging material auxiliary materials through volatile substance analysis.

[0004] As the market demands increasingly higher quality from paper packaging materials for alcoholic beverages, there is a need to find a more accurate and effective method for detecting volatile substances in these materials, thereby enabling a more precise assessment of their quality. Summary of the Invention

[0005] In order to more accurately and effectively identify the quality of paper packaging material accessories, this application provides a method for determining volatile substances in paper packaging material accessories.

[0006] This application provides a method for determining volatile substances in paper outer packaging material auxiliary materials, using the following technical solution:

[0007] A method for determining volatile substances in paper packaging material auxiliary materials includes the following steps:

[0008] (1) Weigh out a paper outer packaging material auxiliary sample and send the volatile substances in the paper outer packaging material auxiliary sample into a gas chromatograph-mass spectrometer for non-target detection using headspace injection. Perform qualitative and quantitative analysis on the volatile substances in the paper outer packaging material auxiliary sample.

[0009] (2) In chronological order, the volatile substances of the paper packaging material auxiliary samples are evaluated by smelling, and a quality discrimination model for the paper packaging material auxiliary samples is established. The sensory evaluation results are substituted into the quality discrimination model to calculate the irritant odor dissipation score of the paper packaging material auxiliary samples. The irritation of the volatile substances in the paper packaging material auxiliary samples is analyzed based on the irritant odor dissipation score. The higher the irritant odor dissipation score of the paper packaging material auxiliary samples, the less irritating the volatile substances in the paper packaging material auxiliary samples, and the better the quality of the paper packaging material auxiliary samples.

[0010] Preferably, in step (2), the sensory evaluation of the volatile substances in the paper packaging material auxiliary sample by smelling in chronological order and the establishment of a quality discrimination model for the paper packaging material auxiliary sample, the substitution of the sensory evaluation results into the quality discrimination model for the paper packaging material auxiliary sample to calculate the irritant odor dissipation score of the paper packaging material auxiliary sample, and the analysis of the irritancy of the volatile substances in the paper packaging material auxiliary sample based on the irritant odor dissipation score of the paper packaging material auxiliary sample include:

[0011] According to the chronological order, at each preset time point, the odor of the paper outer packaging material auxiliary sample was detected by manual smelling and scored according to the strength of the irritation, so as to obtain the score value corresponding to each preset time point.

[0012] The average decay rate of the irritant odor was calculated based on the scoring value, and a quality discrimination model for paper outer packaging material auxiliary samples was established.

[0013] Substituting the score and the average decay rate of the irritant odor into the quality discrimination model of the paper outer packaging material auxiliary sample, the irritant odor dissipation score of the paper outer packaging material auxiliary sample is calculated.

[0014] Preferably, in step (2), the sensory evaluation of the volatile substances in the paper packaging material auxiliary sample by smelling in chronological order and the establishment of a quality discrimination model for the paper packaging material auxiliary sample, the substitution of the sensory evaluation results into the quality discrimination model for the paper packaging material auxiliary sample to calculate the irritant odor dissipation score of the paper packaging material auxiliary sample, and the analysis of the irritancy of the volatile substances in the paper packaging material auxiliary sample based on the irritant odor dissipation score of the paper packaging material auxiliary sample include:

[0015] In chronological order, at time points 0h, 24h, 48h, 72h, 168h, and 226h, the odor of the paper outer packaging material auxiliary samples was detected by manual smelling and scored according to the strength of irritation. The score obtained at 0h was A1, the score obtained at 24h was A2, the score obtained at 48h was A3, the score obtained at 72h was A4, the score obtained at 168h was A5, and the score obtained at 226h was A6.

[0016] The attenuation value B1 of the paper outer packaging material auxiliary sample at 24 hours is calculated using formula B1 = A1 - A2; the attenuation value B2 of the paper outer packaging material auxiliary sample at 48 hours is calculated using formula B2 = A1 - A3; the attenuation value B3 of the paper outer packaging material auxiliary sample at 72 hours is calculated using formula B3 = A1 - A4; the attenuation value B4 of the paper outer packaging material auxiliary sample at 168 hours is calculated using formula B4 = A1 - A5; and the attenuation value B5 of the paper outer packaging material auxiliary sample at 226 hours is calculated using formula B5 = A1 - A6.

[0017] The average decay rate of the pungent odor of the paper outer packaging material auxiliary sample from 0 to 24 hours was calculated using the formula C1 = B1 / 24; the average decay rate of the pungent odor of the paper outer packaging material auxiliary sample from 0 to 48 hours was calculated using the formula C2 = B2 / 48; the average decay rate of the pungent odor of the paper outer packaging material auxiliary sample from 0 to 72 hours was calculated using the formula C3 = B3 / 72; the average decay rate of the pungent odor of the paper outer packaging material auxiliary sample from 0 to 168 hours was calculated using the formula C4 = B4 / 168; and the average decay rate of the pungent odor of the paper outer packaging material auxiliary sample from 0 to 226 hours was calculated using the formula C5 = B5 / 226.

[0018] The odor of the paper packaging material auxiliary sample is detected by manual smelling and scored on a 100-point scale according to the strength of the irritation. The weight of C1 is 5, C2 is 4, C3 is 3, C4 is 2, and C5 is 1. A quality discrimination model for the paper packaging material auxiliary sample is established as M = 100 - A1 + 5*C1 + 4*C2 + 3*C3 + 2*C4 + 1*C5, where M is the irritation odor dissipation score of the paper packaging material auxiliary sample.

[0019] The irritant odor dissipation score of the paper outer packaging material auxiliary sample was calculated using the quality discrimination model M = 100 - A1 + 5*C1 + 4*C2 + 3*C3 + 2*C4 + 1*C5.

[0020] Preferably, in step (1), the mass of the paper outer packaging material auxiliary sample weighed is 1-3g;

[0021] Preferably, in step (1), the mass of the paper outer packaging material auxiliary sample weighed is 2g.

[0022] Preferably, in step (1), the method of sending volatile substances in the paper outer packaging material auxiliary sample into a gas chromatograph-mass spectrometer for non-targeted detection using headspace sampling includes: placing the weighed paper outer packaging material auxiliary sample into a headspace vial, adding sodium chloride and deionized water to the headspace vial, placing the headspace vial into a headspace sampler, equilibrating the headspace vial at 80-100°C for 15-30 minutes, extracting the gas from the headspace vial and sending it into the gas chromatograph-mass spectrometer for detection, comparing the detected spectrum with the spectrum in the NIST spectral library to qualitatively detect the volatile substances in the paper outer packaging material auxiliary sample; and semi-quantitatively detecting the volatile substances.

[0023] Preferably, the headspace vial is placed in a headspace sampler, the headspace vial is equilibrated at 90°C for 15 min, and the gas inside the headspace vial is extracted and entered into a gas chromatograph-mass spectrometer for detection.

[0024] Preferably, the mass-to-volume ratio of the paper outer packaging material sample, the sodium chloride, and the deionized water is 1:(0.5-1):(2.5-4);

[0025] Preferably, the mass-to-volume ratio of the paper outer packaging material sample, the sodium chloride, and the deionized water is 1:0.5:2.5;

[0026] Preferably, the parameters of the headspace sampler are set as follows: sampling needle temperature 80-120℃, feed line temperature 270-280℃, injection pressure 102-104 kPa, pressurization time 1.0-1.5 min, injection time 0.03-0.05 min, needle withdrawal time 0.3-0.5 min, and injection volume 1-1.2 mL;

[0027] Preferably, the parameters of the headspace sampler are set as follows: sampling needle temperature is 100℃, feed line temperature is 280℃, injection pressure is 103kPa, pressurization time is 1.0min, injection time is 0.05min, needle withdrawal time is 0.3min, and injection volume is 1mL.

[0028] Preferably, in step (1), the gas chromatography parameters are set as follows: the column is HP-5MS (30m×250μm×0.25μm), the injection port temperature is 240~260℃, the carrier gas is helium, the carrier gas flow rate is 1~2mL / min, splitless injection is used, and the injection volume is 900~1000μL;

[0029] The heating program is as follows: the initial temperature is 50℃, hold for 0.2 to 2 min, then increase the temperature to 180℃ at 2 to 10℃ / min, then increase the temperature to 280℃ at 15 to 35℃ / min, and hold for 0 to 10 min;

[0030] Preferably, in step (1), the gas chromatography parameters are set as follows: the column is HP-5MS (30m×250μm×0.25μm), the injection port temperature is 250℃, the carrier gas is helium, the carrier gas flow rate is 1mL / min, splitless injection is used, and the injection volume is 1000μL.

[0031] The heating program is as follows: the initial temperature is 50℃, held for 0.5 min; then the temperature is increased to 180℃ at 8℃ / min, and then increased to 280℃ at 15℃ / min, held for 1 min.

[0032] Preferably, in step (1), the mass spectrometry parameters are set as follows: ion source temperature is 220-240℃, quadrupole temperature is 145-155℃, interface temperature is 275-285℃, EI source is 70eV, scanning mode is SCAN, mass range is 30-500Amu, and solvent delay is 0min.

[0033] Preferably, in step (1), the mass spectrometry parameters are set as follows: ion source temperature is 230℃, quadrupole temperature is 150℃, interface temperature is 280℃, EI source is 70eV, scanning mode is SCAN, mass range is 30~500Amu, and solvent delay is 0min.

[0034] This application has the following beneficial technical effects:

[0035] (1) This application combines instrument detection method with volatile substance irritant odor analysis method to comprehensively, accurately and effectively detect volatile substances in paper outer packaging material auxiliary materials, thereby enabling the selection of better quality paper outer packaging material auxiliary materials for use in wine packaging materials based on the test results.

[0036] (2) This application can qualitatively identify the volatile substances in paper packaging materials by non-targeted detection of volatile substances in paper packaging materials, and can detect the volatile substances in paper packaging materials more accurately and comprehensively. Attached Figure Description

[0037] Figure 1 This is the total ion chromatogram of a 1g paper outer packaging material auxiliary sample from Example 2;

[0038] Figure 2 This is the total ion chromatogram of the 2g paper outer packaging material auxiliary sample in Example 2;

[0039] Figure 3 This is the total ion chromatogram of the 3g paper outer packaging material auxiliary sample in Example 2;

[0040] Figure 4 This is the total ion chromatogram of the paper outer packaging material auxiliary sample detected at an equilibrium temperature of 40°C in Example 3;

[0041] Figure 5 This is the total ion chromatogram of the paper outer packaging material auxiliary sample detected at an equilibrium temperature of 60°C in Example 3;

[0042] Figure 6 This is the total ion chromatogram of the paper outer packaging material auxiliary sample detected at an equilibrium temperature of 80°C in Example 3;

[0043] Figure 7 This is the total ion chromatogram of the paper outer packaging material auxiliary sample detected at an equilibrium temperature of 90°C in Example 3;

[0044] Figure 8 This is the total ion chromatogram of the paper outer packaging material auxiliary sample detected at an equilibrium temperature of 100°C in Example 3;

[0045] Figure 9 This is the total ion chromatogram of the paper outer packaging material auxiliary sample after equilibration for 15 minutes in Example 4;

[0046] Figure 10 This is the total ion chromatogram of the paper outer packaging material auxiliary sample after equilibration for 30 minutes in Example 4;

[0047] Figure 11This is the total ion chromatogram of the paper outer packaging material auxiliary sample after equilibration for 45 minutes in Example 4;

[0048] Figure 12 This is the total ion flow chromatogram of condition 1 as the heating program in Example 5;

[0049] Figure 13 This is the total ion flow chromatogram of condition 2 in Example 5 as the temperature ramping program;

[0050] Figure 14 This is the total ion flow chromatogram of condition 3 in Example 5 as the heating program;

[0051] Figure 15 This is the total ion chromatogram for the detection of volatiles in the gelatin in Example 6;

[0052] Figure 16 This is the total ion chromatogram for the detection of volatiles in the mounting adhesive in Example 6;

[0053] Figure 17 This is the total ion chromatogram for the detection of volatiles in the adhesive in Example 6;

[0054] Figure 18 This is the total ion chromatogram for the detection of volatiles from the paper / plastic interface adhesive in Example 6. Detailed Implementation

[0055] Currently, existing technologies include methods for detecting volatile substances in adhesives used in food-grade cigarette packaging materials using solid-phase microextraction combined with gas chromatography-mass spectrometry (GC-MS). However, this method can only detect a few volatile organic compounds in that specific adhesive. It is not applicable to other types of adhesives, and the range of detectable substances is limited. It cannot identify other components within the volatile substances, and therefore cannot provide a comprehensive, accurate, and effective detection of volatile substances in adhesives. Furthermore, because this method uses headspace solid-phase microextraction for sample introduction, it consumes a large number of extraction heads. Additionally, instrumental analysis alone cannot provide a comprehensive analysis of the volatile substances in adhesives. For example, even if an adhesive is found to have no odorous substances by instrumental analysis, if its volatile substances have a strong, pungent odor, then the overall quality of this adhesive is low, making it unsuitable for use in alcoholic beverage packaging materials. On the other hand, existing technologies also assess adhesive quality by identifying pungent odors. However, directly smelling the adhesive is too simplistic and prone to significant errors. For example, an adhesive may have a mild pungent odor but contain long-lasting volatile odor substances, making it inaccurate to judge the quality of the adhesive by smell.

[0056] In the actual production process of paper packaging materials for alcoholic beverages, it is necessary to select the paper packaging material with the best overall quality from a variety of paper packaging material auxiliary materials. This application, through non-targeted detection of volatile substances in paper packaging material auxiliary materials, can achieve a more comprehensive and accurate detection of volatile substances. At the same time, through odor irritation detection of paper packaging material auxiliary materials, it is possible to further detect and analyze the volatile substances in paper packaging material auxiliary materials. The combination of these two methods can enable the selection of higher quality paper packaging material auxiliary materials for use in alcoholic beverage packaging materials.

[0057] The present application will be further described below with reference to the embodiments.

[0058] Instruments: Gas chromatograph-mass spectrometer (GC-MS), purchased from Agilent Technologies, USA; headspace sampler, model GC Sampler 80, purchased from Agilent Technologies, USA.

[0059] The paper packaging material accessories in this application are: mounting adhesive (water-based); jelly adhesive (animal-based); laminating adhesive (thermoplastic polymer); bonding adhesive (plant-based); and paper / plastic interface adhesive (thermoplastic polymer). All paper packaging material accessories in this application are commercially available products.

[0060] In this application, "odorous substances" refers to substances that emit foul odors, ammonia smells, gasoline smells, or other odors that cause discomfort to the human body. Examples include toluene and thiols.

[0061] Example 1

[0062] In this embodiment, a mounting adhesive with a high number of volatile components and a complex composition was selected as an auxiliary material sample for paper outer packaging material volatile content detection.

[0063] (1) Weigh the paper outer packaging material auxiliary sample and send the volatile substances in the paper outer packaging material auxiliary sample into the gas chromatograph-mass spectrometer for non-target detection by headspace injection. Perform qualitative and quantitative analysis on the volatile substances in the paper outer packaging material auxiliary sample.

[0064] Specifically, 2g of paper packaging material auxiliary material sample was weighed and placed into a headspace vial. 1g of sodium chloride and 5mL of deionized water were then added to the headspace vial. The headspace vial was then equilibrated at 90℃ for 15 minutes. The gas inside the headspace vial was extracted and injected into a gas chromatography-mass spectrometry (GC-MS) instrument for detection. The detected chromatogram was compared with chromatograms in the NIST database to qualitatively determine the volatile substances in the paper packaging material auxiliary material sample. A semi-quantitative detection method was also used to perform semi-quantitative detection of the paper packaging material auxiliary material sample.

[0065] The semi-quantitative detection method involves determining the standard compounds needed for semi-quantitative analysis based on the compounds identified qualitatively. The standard compounds are selected from substances with similar physicochemical properties to the compounds to be semi-quantitatively analyzed and that do not chemically react with them. For example, ethyl acetate is used as the standard compound for qualitatively identified esters; toluene is used for aromatic hydrocarbons; and longifolene is used for alkenes. The relative content of the compound to be semi-quantitatively analyzed is calculated using the ratio of its peak area to the peak area of ​​the compound to be semi-quantitatively analyzed, thus enabling semi-quantitative detection of volatile substances in paper packaging material auxiliary materials.

[0066] The headspace sampler parameters were set as follows: sampling needle temperature 100℃, feed line temperature 280℃, injection pressure 103kPa, pressurization time 1.0min, injection time 0.05min, needle withdrawal time 0.3min, and injection volume 1mL.

[0067] The parameters for gas chromatography were set as follows: the column was HP-5MS (30m×250μm×0.25μm), the injection port temperature was 250℃, the carrier gas was helium, the carrier gas flow rate was 1mL / min, splitless injection was used, and the injection volume was 1000μL.

[0068] The heating program is as follows: the initial temperature is 50℃, held for 0.5 min; then the temperature is increased to 180℃ at 8℃ / min, and then increased to 280℃ at 15℃ / min, held for 1 min.

[0069] The mass spectrometry parameters were set as follows: ion source temperature 230℃, quadrupole temperature 150℃, interface temperature 280℃, EI source 70eV, scan mode SCAN, mass range 30~500Amu, solvent delay 0min.

[0070] The semi-quantitative detection of the volatile content of the mounting adhesive in this embodiment is shown in Table 1.

[0071] Table 1. Results of volatile content detection in mounting adhesives

[0072] Compound Name Substance content (mg / kg) L-alpha-pinene 4.39 L-beta-pinene 1.47 β-pinene 1.07 Phyllanthrene 0.30 γ-terpinene 0.60 Terpinene 0.76 aloe-ocimene 0.24 α-Pinoresinol 0.56 longleaf pinene 0.44 (+)-Longylcycloene 0.58 Longleafene 2.17

[0073] As can be seen from Table 1, the detection method of this application can identify the chemical composition of volatile substances in mounting adhesive, perform semi-quantitative detection, and perform non-targeted detection of volatile substances in mounting adhesive. The quality of mounting adhesive can be determined by whether the chemical composition of volatile substances contains long-lasting odorous substances.

[0074] The sampling method used in this application is headspace sampling, which eliminates the need for an extraction head, thus reducing extraction head consumption. Furthermore, this method is a non-targeted detection method for volatile substances, enabling qualitative and quantitative analysis of all volatile substances in paper packaging materials and accessories. This provides a more comprehensive range of detected substances and allows for more effective assessment of the quality of paper packaging materials and accessories.

[0075] (2) In chronological order, the volatile substances of the paper packaging material auxiliary samples are evaluated by smelling, and a quality discrimination model for the paper packaging material auxiliary samples is established. The sensory evaluation results are substituted into the quality discrimination model to calculate the irritant odor dissipation score of the paper packaging material auxiliary samples. The irritation of the volatile substances in the paper packaging material auxiliary samples is analyzed based on the irritant odor dissipation score. The higher the irritant odor dissipation score of the paper packaging material auxiliary samples, the less irritating the volatile substances in the paper packaging material auxiliary samples, and the better the quality of the paper packaging material auxiliary samples.

[0076] Specifically, in chronological order, the odor of paper packaging material samples was detected by manual smelling at time points 0h, 24h, 48h, 72h, 168h, and 226h, and scored according to the strength of irritation. The score obtained at 0h was A1, at 24h it was A2, at 48h it was A3, at 72h it was A4, at 168h it was A5, and at 226h it was A6.

[0077] Furthermore, the above-mentioned method of detecting the odor of paper outer packaging material auxiliary samples by manual smelling and scoring them according to the strength of irritation includes: an evaluation group composed of 5 evaluators with national level 2 wine taster or above professional qualifications, with each of the 5 evaluators scoring the paper outer packaging material auxiliary samples, and the average value being taken as the final score.

[0078] The attenuation value B1 of the paper packaging material auxiliary sample at 24 hours was calculated using formula B1 = A1 - A2; the attenuation value B2 of the paper packaging material auxiliary sample at 48 hours was calculated using formula B2 = A1 - A3; the attenuation value B3 of the paper packaging material auxiliary sample at 72 hours was calculated using formula B3 = A1 - A4; and the attenuation value B4 = A1 - A5 was calculated using formula B5.

[0079] The attenuation value B4 of the paper outer packaging material auxiliary sample at 168h was calculated; the attenuation value B5 of the paper outer packaging material auxiliary sample at 226h was calculated using the formula B5=A1-A6.

[0080] The average decay rate of the irritant odor of the paper packaging material auxiliary sample from 0 to 24 hours was calculated using the formula C1 = B1 / 24; the average decay rate of the irritant odor of the paper packaging material auxiliary sample from 0 to 48 hours was calculated using the formula C2 = B2 / 48; the average decay rate of the irritant odor of the paper packaging material auxiliary sample from 0 to 72 hours was calculated using the formula C3 = B3 / 72; the average decay rate of the irritant odor of the paper packaging material auxiliary sample from 0 to 168 hours was calculated using the formula C4 = B4 / 168; and the average decay rate of the irritant odor of the paper packaging material auxiliary sample from 0 to 226 hours was calculated using the formula C5 = B5 / 226.

[0081] The odor of paper packaging material samples was detected by manual olfaction and scored on a 100-point scale according to the strength of the irritation. Specifically, the scores were divided into four levels: none, slight, moderate, and severe. The score for none was 0 points, for slight it was 30 points, for moderate it was 50 points, and for severe it was 100 points.

[0082] The earlier the time frame, the greater the impact of the average decay rate of the paper packaging material auxiliary samples on the quality of the paper packaging material auxiliary samples. Therefore, the weight of C1 is 5, the weight of C2 is 4, the weight of C3 is 3, the weight of C4 is 2, and the weight of C5 is 1. A quality discrimination model for paper packaging material auxiliary samples is established: M = 100 - A1 + 5*C1 + 4*C2 + 3*C3 + 2*C4 + 1*C5, where M is the odor dissipation score of the paper packaging material auxiliary samples.

[0083] The irritant odor dissipation score of paper packaging material auxiliary samples was calculated using the quality discrimination model M = 100 - A1 + 5*C1 + 4*C2 + 3*C3 + 2*C4 + 1*C5.

[0084] Understandably, the larger the M value, the better the quality of the paper packaging material auxiliary sample. In the actual testing process, the M values ​​of different types of paper packaging material auxiliary materials can be compared, and the paper packaging material auxiliary materials with larger M values ​​can be selected. Combined with the instrumental analysis results of volatile substances in the paper packaging material auxiliary materials, the paper packaging material auxiliary materials with the best quality can be selected and applied to wine packaging materials.

[0085] Example 2 investigates the effect of weighing different masses of paper packaging material auxiliary samples on the test results.

[0086] This embodiment investigates the effect of weighing different masses of paper packaging material auxiliary samples on the detection results. The masses of the weighed paper packaging material auxiliary samples included 1g, 2g, and 3g. 1g, 2g, and 3g of paper packaging material auxiliary samples were weighed and tested respectively, with the remaining detection steps being the same as in Example 1. The total ion chromatogram of the 1g paper packaging material auxiliary sample is shown below. Figure 1 As shown, the total ion chromatogram of a 2g sample of paper outer packaging material auxiliary material is as follows. Figure 2 As shown, the total ion chromatogram of a 3g sample of paper outer packaging material auxiliary material is as follows. Figure 3 As shown. From Figures 1-3 It can be seen that the characteristic peaks of volatile substances in the three different weights of paper packaging materials are well separated. The total peak area and number of characteristic peaks of the three different weights of paper packaging materials are shown in Table 2.

[0087] Table 2. Total peak area and number of characteristic peaks of three different quality paper outer packaging material auxiliary samples.

[0088]

[0089] As can be seen from Table 2, when the weight of the paper packaging material auxiliary sample is 2g or 3g, its total peak area is much higher than that when the weight of the paper packaging material auxiliary sample is 1g. This indicates that adjusting the weight of the paper packaging material auxiliary sample can effectively increase the total peak area detected, which helps to improve the accuracy of the detection results of volatile substances in the paper packaging material auxiliary sample.

[0090] Example 3 investigates the effect of different temperatures on the test results during headspace flask equilibration.

[0091] This embodiment investigates the effect of different temperatures during headspace equilibration on the detection results. The headspace equilibration temperatures included 40℃, 60℃, 80℃, 90℃, and 100℃. The headspace bottles were equilibrated for 15 minutes at each of these temperatures, and the remaining detection steps were the same as in Example 1. The total ion chromatogram for the paper packaging material sample at 40℃ is shown below. Figure 4 As shown, the total ion chromatogram of the paper outer packaging material auxiliary sample at 60℃ is as follows. Figure 5 As shown, the total ion chromatogram for the paper outer packaging material auxiliary sample at 80℃ is as follows. Figure 6 As shown, the total ion chromatogram for the detection of paper outer packaging material auxiliary samples at 90℃ is as follows. Figure 7 As shown, the total ion chromatogram for the paper outer packaging material auxiliary sample at 100℃ is as follows. Figure 8 As shown. From Figures 4-5It can be seen that when the equilibrium temperature is 40℃ and 60℃, the number of characteristic peaks in the paper packaging material auxiliary samples is very small and the abundance is very low, making it virtually impossible to detect volatile substances in the paper packaging material auxiliary samples. Figures 6-8 It can be seen that when the equilibrium temperature is 80℃, 90℃, and 100℃, obvious characteristic peaks appear, and the separation effect of the characteristic peaks is good, enabling qualitative detection. When the equilibrium temperature is 90℃, the abundance of each characteristic peak is greater than that at 80℃ and 100℃, and the semi-quantitative effect is better. This indicates that adjusting the equilibrium temperature can effectively improve the qualitative and semi-quantitative detection effect of paper packaging material auxiliary samples.

[0092] Example 4: Effect of different headspace equilibration times on test results

[0093] This embodiment investigates the effect of different headspace vial equilibration times on the detection results. The headspace vial equilibration times included 15 min, 30 min, and 45 min. The headspace vials were equilibrated at 90°C for 15 min, 30 min, and 45 min, respectively, and the remaining detection steps were the same as in Example 1. The total ion chromatogram of the paper outer packaging material sample after equilibration for 15 min is shown below. Figure 9 As shown, the total ion chromatogram of the paper packaging material auxiliary sample after equilibration for 30 minutes is as follows. Figure 10 As shown, the total ion chromatogram of the paper packaging material auxiliary sample after equilibration for 45 minutes is as follows. Figure 11 As shown. From Figures 9-11 It can be seen that when the equilibration time is 15 min, 30 min, and 45 min, obvious characteristic peaks appear, and the separation effect of the characteristic peaks is good, which can be used for qualitative detection. The total peak area and number of characteristic peaks of the paper outer packaging material auxiliary samples at three different equilibration times are shown in Table 3.

[0094] Table 3. Total peak area and number of characteristic peaks for paper packaging material auxiliary samples with three different equilibrium times.

[0095] Equilibrium time Total peak area Number of characteristic peaks 15min 466345325 75 30min 468527918 70 45min 421147525 62

[0096] Table 3 shows that the total peak area is relatively similar at equilibration times of 15 min and 30 min, and is higher than that at equilibration time of 45 min. As the equilibration time increases, the number of characteristic peaks in the paper packaging material auxiliary samples gradually decreases. This indicates that adjusting the equilibration time of the paper packaging material auxiliary samples can effectively increase the total peak area and the number of characteristic peaks, thus improving the accuracy of qualitative and semi-quantitative detection results of volatile substances in these samples.

[0097] Example 5 investigates the effect of different column temperature programs on detection results.

[0098] To investigate the effects of different chromatographic parameters on the detection results, this embodiment sets three different temperature programs, as shown in Table 4.

[0099] Table 4. Conditions for three different heating programs

[0100]

[0101] The tests were performed under three different temperature ramping conditions, with the remaining testing steps being the same as in Example 1. The total ion chromatogram for the test under condition 1 is shown below. Figure 12 As shown, the total ion chromatogram for detection under condition 2 is as follows. Figure 13 As shown, the total ion chromatogram for detection under condition 3 is as follows. Figure 14 As shown. From Figures 12-14 It can be seen that all three heating program conditions have a good separation effect on the characteristic peaks of volatile substances in paper packaging material auxiliary samples. However, the abundance of condition 2 is much higher than that of conditions 1 and 3. This indicates that condition 2 has a higher response to the detection of volatile substances in paper packaging material auxiliary samples, which is more conducive to the detection of volatile substances in paper packaging material auxiliary samples and the detection results are more accurate.

[0102] As can be seen from Examples 2 to 5, any change in the headspace parameters and GC-MS instrument parameter settings in the detection method of this application will affect the detection results. Through optimization of headspace parameter conditions and instrument parameter settings, this application can finally establish a method for non-targeted detection of paper outer packaging material auxiliary samples.

[0103] Example 6

[0104] The method for detecting volatiles in paper packaging material auxiliary samples in Example 1 of this application can perform non-targeted detection on various types of paper packaging material auxiliary samples. The mounting adhesive in Example 1 is the paper packaging material auxiliary sample with the highest and most complex volatile components. The method that can effectively detect mounting adhesive is also applicable to other paper packaging material auxiliary samples with fewer volatile components than mounting adhesive. The following uses jelly adhesive, laminating adhesive, interlocking adhesive, and paper / plastic interface adhesive as examples to apply the method for detecting volatiles in paper packaging material auxiliary samples in Example 1 to detect volatile substances in jelly adhesive, laminating adhesive, interlocking adhesive, and paper / plastic interface adhesive, respectively. The total ion chromatogram for volatile substance detection in jelly adhesive is shown below. Figure 15 As shown in Table 5, the volatile matter content (semi-quantitative) detection results are presented. The total ion chromatogram for the detection of volatile matter in the mounting adhesive is shown below. Figure 16 As shown in Table 6, the volatile content (semi-quantitative) detection results are presented. The total ion chromatogram for the volatile content detection of the adhesive is shown below. Figure 17 As shown in Table 7, the volatile matter content (semi-quantitative) detection results are presented. The total ion chromatogram for volatile matter detection in paper / plastic interface adhesive is shown below. Figure 18As shown in Table 8, the volatile matter content (semi-quantitative) detection results are presented.

[0105] Table 5. Results of volatile content detection in gelatin.

[0106] Compound Name Substance content (mg / kg) Butyl propionate 1.40 Butyl butyrate 0.48 Dimethyl succinate 2.24 Dimethyl glutarate 4.29 dimethyl adipic acid 0.23

[0107] Table 6 shows the test results of the volatile content of the mounting adhesive.

[0108] Compound Name Substance content (mg / kg) Cumene 0.15 Butyl butyrate 0.34 Isooctyl alcohol 0.28 Isooctyl acetate 0.51 6-Methylheptyl acrylate 1.83 Butyl butyrate 4.02

[0109] Table 7 Results of volatile content detection of adhesive tape

[0110] Compound Name Substance content (mg / kg) o-Isopropylbenzene 16.73 Isooctyl acetate 1.67 6-Methylheptyl acrylate 0.01 (+)-Longylcycloene 1.24 Isopyrene 0.43 Longleafene 2.95

[0111] Table 8. Detection Results of Volatile Matter Content in Paper / Plastic Interface Adhesive

[0112] Compound Name Substance content (mg / kg) 6-Methylheptyl acrylate 1.69 Butyl butyrate 3.44 Isooctyl acetate 0.64 Butyl propionate 0.17

[0113] from Figures 15-18 It can be seen that the detection method in Example 1 can perform qualitative detection on four different types of paper packaging material accessories, and can effectively separate each characteristic peak. Tables 5-8 show that the detection method in Example 1 can perform semi-quantitative detection on four different types of paper packaging material accessories, and can detect the content of different volatile substances in the paper packaging material accessories. This indicates that the detection method in Example 1 of this application is applicable to detecting other paper packaging material accessories with fewer volatile substances than the mounting adhesive, and can perform non-targeted detection on various types of paper packaging material accessories.

[0114] Furthermore, the method for detecting volatile substances in paper packaging material auxiliary samples from Example 1 was applied to detect volatile substances in more different types of paper packaging material auxiliary samples. The detection results are shown in Table 9.

[0115] Table 9. Results of Volatile Matter Detection in Different Paper Packaging Material Auxiliaries

[0116]

[0117]

[0118] As can be seen from Table 9, the detection method in Example 1 of this application can qualitatively detect volatile substances in various types of paper packaging material auxiliary materials, and can effectively identify and analyze the composition of volatile substances in paper packaging material auxiliary material samples. This indicates that the detection method of this application can be applied to the detection and analysis of volatile substances in different paper packaging material auxiliary material samples.

[0119] This application utilizes non-targeted detection and analysis of volatile substances in paper packaging materials and auxiliary materials, as well as irritation detection and analysis of these volatile substances. By combining instrumental analysis and odor irritation analysis, it is possible to accurately and effectively detect the volatile substances in various types of paper packaging materials and auxiliary materials. Based on the test results, higher-quality paper packaging materials and auxiliary materials can be selected for use in wine packaging materials.

[0120] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A method for determining volatile substances in a paper outer packaging material auxiliary material, characterized by, The method comprises the following steps: (1) a paper outer packaging material auxiliary sample is weighed, and volatile substances in the paper outer packaging material auxiliary sample are sent into a gas chromatography-mass spectrometer for non-target detection by using a headspace sampling method, so as to perform qualitative and quantitative analysis on the volatile substances in the paper outer packaging material auxiliary sample; The mass of the paper outer packaging material auxiliary sample is 1-3 g; The non-target detection in the gas chromatography-mass spectrometer comprises the following steps: the weighed paper outer packaging material auxiliary sample is placed into a headspace bottle, sodium chloride and deionized water are added into the headspace bottle, the headspace bottle is placed into a headspace sampler, the headspace bottle is balanced at 80-100 DEG C for 15-30 min, gas in the headspace bottle is extracted and detected in the gas chromatography-mass spectrometer, and the detected spectrum is compared with a spectrum in a NIST spectrum library, so as to perform qualitative detection on the volatile substances in the paper outer packaging material auxiliary sample; and the volatile substances are semi-quantitatively detected; (2) according to time sequence, the smell of the paper outer packaging material auxiliary sample is detected by using artificial sniffing at 0 h, 24 h, 48 h, 72 h, 168 h and 226 h, and a score is given according to the strength of stimulation, the score value obtained at 0 h is A1, the score value obtained at 24 h is A2, the score value obtained at 48 h is A3, the score value obtained at 72 h is A4, the score value obtained at 168 h is A5, and the score value obtained at 226 h is A6; The attenuation value B1 of the paper outer packaging material auxiliary sample at 24 h is calculated by using the formula B1=A1-A2; the attenuation value B2 of the paper outer packaging material auxiliary sample at 48 h is calculated by using the formula B2=A1-A3; the attenuation value B3 of the paper outer packaging material auxiliary sample at 72 h is calculated by using the formula B3=A1-A4; the attenuation value B4 of the paper outer packaging material auxiliary sample at 168 h is calculated by using the formula B4=A1-A5; and the attenuation value B5 of the paper outer packaging material auxiliary sample at 226 h is calculated by using the formula B5=A1-A6; The average stimulation smell attenuation rate C1 of the paper outer packaging material auxiliary sample at 0-24 h is calculated by using the formula C1=B1 / 24; the average stimulation smell attenuation rate C2 of the paper outer packaging material auxiliary sample at 0-48 h is calculated by using the formula C2=B2 / 48; the average stimulation smell attenuation rate C3 of the paper outer packaging material auxiliary sample at 0-72 h is calculated by using the formula C3=B3 / 72; the average stimulation smell attenuation rate C4 of the paper outer packaging material auxiliary sample at 0-168 h is calculated by using the formula C4=B4 / 168; and the average stimulation smell attenuation rate C5 of the paper outer packaging material auxiliary sample at 0-226 h is calculated by using the formula C5=B5 / 226; The paper outer packaging material auxiliary material sample is detected by artificial smelling, and a score is given according to the strength of stimulation, which is a percentage score, and the weight of C1 is 5, the weight of C2 is 4, the weight of C3 is 3, the weight of C4 is 2, and the weight of C5 is 1, and a quality discrimination model M=100-A1+5*C1+4*C2+3*C3+2*C4+1*C5 of the paper outer packaging material auxiliary material sample is established, wherein M is a dissipation score of stimulating odor of the paper outer packaging material auxiliary material sample. The quality discrimination model M=100-A1+5*C1+4*C2+3*C3+2*C4+1*C5 of the paper outer packaging material auxiliary material sample is used to calculate a dissipation score of stimulating odor of the paper outer packaging material auxiliary material sample, and the stimulating property of volatile substances of the paper outer packaging material auxiliary material sample is analyzed according to the dissipation score of stimulating odor of the paper outer packaging material auxiliary material sample; the higher the dissipation score of stimulating odor of the paper outer packaging material auxiliary material sample, the smaller the stimulating property of volatile substances of the paper outer packaging material auxiliary material sample, and the better the quality of the paper outer packaging material auxiliary material sample.

2. The method of claim 1, wherein, In step (1), the mass of the paper outer packaging material auxiliary material sample is 2g.

3. The method of claim 2, wherein, In step (1), the volatile substances in the paper outer packaging material auxiliary material sample are sent into a gas chromatography-mass spectrometer by headspace sampling for non-target detection, which includes the following steps: The headspace bottle is placed into a headspace sampler, the headspace bottle is balanced at 90℃ for 15min, and the gas in the headspace bottle is extracted into the gas chromatography-mass spectrometer for detection.

4. The method of claim 1, wherein, The parameters of the headspace sampler are set as follows: the sampling needle temperature is 100℃, the line temperature is 280℃, the sampling pressure is 103kPa, the pressurization time is 1.0min, the sampling time is 0.05min, the needle pulling time is 0.3min, and the sampling amount is 1mL.

5. The method of claim 1, wherein, In step (1), the gas chromatography parameters are set as follows: the chromatographic column is HP-5MS, 30m×250μm×0.25μm, the injection port temperature is 250℃, the carrier gas is helium, the carrier gas flow rate is 1mL / min, the splitless injection is used, and the sampling amount is 1000μL; The temperature rising program is as follows: the initial temperature is 50℃, and the temperature is kept for 0.5min; then the temperature is raised to 180℃ at a rate of 8℃ / min, and then the temperature is raised to 280℃ at a rate of 15℃ / min, and the temperature is kept for 1min.

6. The method of claim 1 or 2, wherein, In step (1), the mass spectrometry parameters are set as follows: the ion source temperature is 230℃, the quadrupole temperature is 150℃, the interface temperature is 280℃, the EI source is 70eV, the scanning mode is SCAN, the mass range is 30-500Amu, and the solvent delay is 0min.

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