Test method and application of skin migration of 20 organophosphorus flame retardants in cosmetic sponges

Abstract

The scheme provides a method and application for testing the skin migration of 20 organophosphorus flame retardants in a cosmetic sponge, comprising the following steps: fixing a cosmetic sponge containing an organophosphorus flame retardant on an electric powder puff device, and using the electric powder puff device to beat an artificial membrane at a set beating frequency; cutting the artificial membrane into pieces, ultrasonically extracting it with acetonitrile, and filtering the extract to obtain a test liquid; placing the test liquid in a liquid chromatography-tandem mass spectrometry to detect the test content of the organophosphorus flame retardant in the artificial membrane; calculating the skin migration amount of the organophosphorus flame retardant based on the test content of the organophosphorus flame retardant in the artificial membrane, the volume of the test liquid, and the area of ​​the artificial membrane, thereby solving the problem of missing skin migration amount in the skin exposure risk assessment of such products and facilitating the accurate assessment of the skin exposure risk of hazardous substances in cosmetic sponge products.

Description

Technical Field

[0001] The present invention relates to the technical field of skin exposure dose assessment for consumer products, and in particular to a test method and application for the skin migration of 20 organophosphorus flame retardants in a cosmetic sponge. Background Art

[0002] In recent years, as people pay more and more attention to environmental and health issues, traditional brominated flame retardants have been subject to many restrictions in production and application due to their potential hazards and toxicity. In this context, organophosphorus flame retardants (OPFRs) have stood out with their own advantages and have become an ideal substitute for brominated flame retardants, and thus become the first choice in the field of industrial additives. OPFRs have excellent flame retardant and plasticizing properties, which makes them widely used in the production process of many products such as plastics, textiles and building materials.

[0003] However, it cannot be ignored that while OPFRs bring convenience to industrial production, they also pose a potential threat to human health. Long-term exposure to OPFRs may cause a series of adverse effects, including interference with the reproductive system, endocrine system, and immune system, and may even increase the risk of cancer.

[0004] In the study of OPFRs, it was found that compared with the environmental exposure route, the presence of OPFRs in consumer products is often easily overlooked. In the past, when people paid attention to the ways in which pollutants enter the human body, they mainly focused on the two routes of oral and inhalation. But now, more and more studies have shown that skin exposure as a way for pollutants to enter the human body is becoming increasingly important. Many studies have confirmed that the risks posed by skin contact with certain harmful substances may be comparable to those posed by inhalation. Therefore, when conducting a comprehensive risk assessment, the risks posed by skin exposure must not be underestimated, especially in some special usage scenarios, and should be given high attention.

[0005] In daily life, cosmetics and various makeup tools have become indispensable consumer goods for people, among which makeup sponges play a vital role in evenly applying makeup. Previous related studies have found that OPFRs are frequently detected in makeup sponges. Since makeup sponges frequently come into contact with facial skin during use, this will undoubtedly cause OPFRs to enter the human body through skin exposure. Unfortunately, as far as the current technical means are concerned, there is no detection method for the skin migration of OPFRs in makeup sponges. This situation directly leads to obvious blank areas in the evaluation of the safety and compliance of makeup sponges, and it is impossible to accurately and comprehensively measure the potential risks that they may bring to users. Summary of the invention

[0006] The purpose of the present invention is to provide a test method and application of the skin migration amount of 20 organophosphorus flame retardants in a cosmetic sponge, adopt an artificial membrane to simulate human facial skin, adopt an electric powder puff to simulate the makeup application process of a cosmetic sponge to create a simulation scene, and adopt liquid chromatography-tandem mass spectrometry to detect the organophosphorus flame retardants in the artificial membrane, so as to realize the test of the skin migration amount of 20 organophosphorus flame retardants in the cosmetic sponge, solve the problem of missing skin migration amount in the skin exposure risk assessment of such products, and help to realize the accurate assessment of the skin exposure risk of harmful substances in cosmetic sponge products.

[0007] To achieve the above objectives, the technical solution provides that a cosmetic sponge containing an organic phosphorus flame retardant is fixed on an electric powder puff device, and the electric powder puff device is used to beat the artificial membrane at a set beating frequency;

[0008] The artificial membrane is cut into pieces and then ultrasonically extracted with acetonitrile, and the extract is filtered to obtain the test solution;

[0009] The test liquid is placed in a liquid chromatography-tandem mass spectrometer to detect the test content of the organophosphorus flame retardant in the artificial membrane;

[0010] The amount of organophosphorus flame retardant skin migration was calculated based on the test content of the organophosphorus flame retardant in the artificial membrane, the volume of the test liquid, and the area of ​​the artificial membrane.

[0011] Compared with the prior art, this technical solution has the following characteristics and beneficial effects:

[0012] This solution uses a cosmetic sponge containing an organophosphorus flame retardant fixed on an electric powder puff, and continuously taps the artificial membrane for 20 to 40 seconds at a specific tapping frequency (2 to 4 times / second). This operation extremely cleverly simulates the contact dynamics between the cosmetic sponge and the skin during actual use. Combined with liquid chromatography-tandem mass spectrometry, it can accurately and efficiently detect the skin migration amount of 20 specific organophosphorus flame retardants in the cosmetic sponge. By simulating the contact method between the cosmetic sponge and the skin during actual use, the test results are more in line with the actual situation, which helps to accurately evaluate the amount of these flame retardants that may migrate to the skin during daily use and protect the health of consumers. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic diagram of the process of a method for testing the skin migration of 20 organophosphorus flame retardants in a cosmetic sponge according to an embodiment of the present invention.

[0014] Figure 2 is a chromatogram of 20 organophosphorus flame retardant standard products according to one embodiment of the present invention.

[0015] Figure 3Graph showing the correlation between the skin migration amount of Example 1 and the tested content of the organophosphorus flame retardant.

[0016] Figure 4 It is a schematic diagram of the correlation between the skin migration amount of Comparative Example 1 and the tested content of the organophosphorus flame retardant.

[0017] In the figure: 1-electric powder puff, 2-makeup sponge, 3-artificial membrane, 4-watch glass. DETAILED DESCRIPTION

[0018] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.

[0019] It is to be understood that the term "one" should be understood as "at least one" or "one or more", that is, in one embodiment, the number of an element may be one, while in another embodiment, the number of the element may be multiple, and the term "one" should not be understood as a limitation on the quantity.

[0020] This protocol provides a test method for the skin migration of 20 organophosphorus flame retardants in cosmetic sponges, including the following steps:

[0021] A cosmetic sponge containing an organic phosphorus flame retardant is fixed on an electric powder puff device, and the electric powder puff device is used to tap the artificial membrane at a set tapping frequency;

[0022] The artificial membrane is cut into pieces and then ultrasonically extracted with acetonitrile, and the extract is filtered to obtain the test solution;

[0023] The test liquid is placed in a liquid chromatography-tandem mass spectrometer to detect the test content of the organophosphorus flame retardant in the artificial membrane;

[0024] The amount of organophosphorus flame retardant skin migration was calculated based on the test content of the organophosphorus flame retardant in the artificial membrane, the volume of the test liquid, and the area of ​​the artificial membrane.

[0025] It should be noted that the detection of the migration of harmful substances in consumer products is a key quality control process that can be used to ensure the safety and compliance of products. The accurate acquisition of the migration of harmful substances in specific usage scenarios is related to the accuracy of exposure assessment. Therefore, this solution specifically constructs a simulated migration scenario for the usage scenario of cosmetic sponges to achieve accurate measurement of the skin migration of organophosphorus flame retardants.

[0026] Specifically, this scheme uses an artificial membrane with a structure similar to human skin to simulate facial skin. When the cosmetic sponge comes into contact with the artificial membrane, it can effectively simulate the migration and residue of harmful substances in the cosmetic sponge on the skin; and this method uses an electric powder puff for patting simulation, which can ensure the consistency of the patting frequency. At the same time, the powder puff can be movably replaced with different cosmetic sponge samples to make the test results comparable. Therefore, this method can better simulate the migration and residue of OPFRs on the face during the use of cosmetic sponges, which is conducive to the accurate assessment of the skin exposure risk of OPFRs in such products.

[0027] The artificial membrane of this scheme is Strat-M TM Artificial membrane, Strat-M TM (Merck Millipore, USA) is an artificial membrane that simulates skin tissue and consists of two layers of polyester sulfone containing synthetic lipids and a polyolefin support layer. TM The artificial membrane has a high degree of structural similarity with facial skin. TM The artificial membrane has a multi-layer structure, and its structure at the microscopic level is somewhat similar to the layered structure of human skin. Human skin is divided into different layers from the outside to the inside, such as the epidermis and dermis. Each layer has different functions and characteristics in terms of the penetration and adsorption of substances. TM The artificial membrane can relatively well simulate the blocking and absorption behaviors of this layered structure on organophosphorus flame retardants, and more accurately simulate the human skin's ability to block and selectively permeate foreign substances as a barrier, making the test results closer to the actual migration of flame retardants on the surface and shallow layers of the skin.

[0028] In some embodiments, the present invention converts Strat-M TM The artificial membrane is fixed in a dish on the operating table to simulate human facial skin, and an electric powder puff is used to tap the artificial membrane at a set tapping frequency.

[0029] This solution selects a set frequency electric powder puff to simulate the process of human body using makeup sponge to pat the face to apply makeup, such as Figure 1 As shown, a cosmetic sponge containing an organophosphorus flame retardant is fixed on an electric puff device and tapped against the artificial membrane in the watch glass; the artificial membrane is extracted by ultrasonic extraction with acetonitrile to extract the organophosphorus flame retardant, and the extracted liquid is filtered. It should be noted that the cosmetic sponge contains any one of the 20 organophosphorus flame retardants or a combination of two or more, which can be adjusted according to the actual test situation.

[0030] In some embodiments, the flapping frequency of the electric powder puff device is 2 to 4 times per second, and the flapping time is 20 to 40 seconds. Preferably, the flapping frequency of the electric powder puff device is 3 times per second, and the flapping time is 30 seconds. This solution sets the flapping frequency and rhythm in accordance with the scene of daily use of makeup sponges for facial makeup. This range is closer to the frequency of manual flapping of makeup sponges by ordinary people when applying makeup normally. In this way, it can more realistically simulate the frequency of contact between the makeup sponge and the skin during the actual makeup process, so that the migration amount of the organophosphorus flame retardant to the artificial membrane (simulated skin) tested later can better reflect the migration that may occur in the actual makeup scene.

[0031] In addition, this solution places an electric powder puff on top of the artificial membrane and continuously taps the surface of the artificial membrane. In the actual makeup process, people usually use a makeup sponge to tap various areas of the face in a relatively uniform manner to achieve uniform makeup. In this way, the organophosphorus flame retardant in the makeup sponge has the opportunity to contact and interact with the surface of the artificial membrane in a relatively uniform manner, thereby more accurately simulating the migration of the flame retardant to the skin (simulated by the artificial membrane) in a real makeup scenario, making the migration amount tested later more representative.

[0032] In some specific embodiments, the diameter of the artificial membrane is 2 cm, the rated power of the electric powder puff is 5 W, and the rated voltage is 5 V. This has the advantage that the electric powder puff provides a relatively stable power output during the test, and the stable power can ensure that the strength and speed of each flapping action are relatively consistent, and there will be no situation where the flapping strength is large or small, the speed is fast or slow, etc. due to unstable power.

[0033] In some embodiments, the present solution cuts the artificial membrane in the beating area into fragments smaller than 5 mm*5 mm in size. This has the advantage that the artificial membrane can be fully immersed in acetonitrile for extraction, thereby more accurately obtaining the content of the organophosphorus flame retardant in the artificial membrane.

[0034] This scheme selects an artificial membrane with a smaller area and sets the electric puff to pat the entire area of ​​the artificial membrane. In addition, this scheme cuts the artificial membrane into pieces to facilitate subsequent extraction with acetonitrile. During the ultrasonic extraction process, smaller samples are more likely to achieve uniform energy transfer and sufficient extraction effects in the ultrasonic equipment. In contrast, larger artificial membranes may have problems such as insufficient local extraction.

[0035] In some embodiments, the present invention uses 1-3 mL of acetonitrile to perform ultrasonic extraction for 25-40 min after the artificial membrane is cut into pieces. Preferably, 1 mL of acetonitrile is used to perform ultrasonic extraction for 30 min.

[0036] This scheme selects acetonitrile to extract the artificial membrane and selects an appropriate amount of acetonitrile as a solvent. The appropriate amount of acetonitrile will not cause some flame retardants to be unable to be fully extracted due to too little solvent, affecting the accuracy of subsequent detection; nor will it cause solvent waste due to too much solvent and may cause unnecessary trouble in subsequent processing steps (such as filtration, etc.). This scheme further uses ultrasonic extraction to promote the transfer of organophosphorus flame retardants from artificial membranes to acetonitrile. During the ultrasonic extraction process, ultrasonic waves continuously act on the mixed system of acetonitrile and artificial membranes, so that the organophosphorus flame retardants on the artificial membrane can be continuously and more fully extracted into acetonitrile.

[0037] In some embodiments, the extract is filtered using a nylon filter to obtain the test solution. Preferably, the extract is filtered using a 0.22 μm nylon filter to obtain the test solution, so as to intercept tiny particles in the extract.

[0038] This scheme uses liquid chromatography-tandem mass spectrometry to detect 20 organophosphorus flame retardants in artificial membranes. Specifically, the chromatographic conditions of liquid chromatography-tandem mass spectrometry are: using a C18 chromatographic column, the column temperature is set to 35~45℃, 0.1% formic acid aqueous solution is used as mobile phase A, methanol mobile phase B is used for gradient elution, the flow rate is 300~400 μL / min, and the injection volume is 1~5μL.

[0039] Preferably, this solution uses a C18 chromatographic column with a particle size of 2.6um and a size of 3*150 mm, and preferably Kinete TM C18 chromatographic column. The C18 chromatographic column selected in this scheme can effectively separate different types of organophosphorus flame retardants by taking into account the differences in the distribution coefficients of 20 organophosphorus flame retardants between the mobile phase and the stationary phase. The 2.6μm particle size filler belongs to the category of smaller particle size in the C18 chromatographic column. The smaller particle size can provide higher column efficiency, that is, more theoretical plates can be achieved within the unit length of the chromatographic column; the 3×150mm column size design ensures sufficient separation length while also having good physical stability.

[0040] Preferably, the chromatographic conditions of the liquid chromatography-tandem mass spectrometry of the present scheme are: using a C18 chromatographic column, the column temperature is set to 40°C, 0.1% formic acid aqueous solution is used as mobile phase A, methanol mobile phase B is used for gradient elution, the flow rate is 400 μL / min, and the injection volume is 2 μL.

[0041] In the embodiment of this scheme, the gradient elution condition table is shown in Table 1 below;

[0042] Table 1 Gradient elution conditions

[0043]

[0044] Correspondingly, the gradient elution conditions are as follows: at 0.01 minutes to 2 minutes, the proportion of mobile phase A is set to 25%, and the proportion of mobile phase B is set to 75%; at 2 to 6 minutes, the proportion of mobile phase A is adjusted to 20%, and the proportion of mobile phase B is adjusted to 80% accordingly; at 6 to 9 minutes, the proportion of mobile phase A is further reduced to 5%, and the proportion of mobile phase B is increased to 95%; at 9 to 10 minutes, the proportion of mobile phase A and mobile phase B remains unchanged, with mobile phase A still being 5% and mobile phase B being 95%; at 10 to 12 minutes, the proportion of mobile phase A is reduced to 0%, and at this time, mobile phase B (methanol) is used entirely, that is, the proportion of mobile phase B is 100%; at 12 to 13 minutes, mobile phase B (methanol) is still used entirely, with mobile phase A being 0% and mobile phase B being 100%; at 13 to 15 minutes, the proportion of mobile phase A is restored to the initial 25%, and the proportion of mobile phase B is restored to 75%. At 15.01 minutes, the elution process stopped.

[0045] In addition, the mass spectrometry conditions of liquid chromatography-tandem mass spectrometry are: the ion source adopts electrospray ionization positive ion mode ESI+, and the mass spectrometry scanning mode is multiple reaction monitoring MRM mode; the gas curtain gas CUR is 30~40Psi; the voltage IS is 5200~5700; the ion source temperature TEM is 480~520°C; the nebulizer gas GS1 is 52~55Psi; the auxiliary gas GS2 is 52~55Psi. Preferably, the ion source adopts electrospray ionization positive ion mode ESI+, and the mass spectrometry scanning mode is multiple reaction monitoring MRM mode; the gas curtain gas CUR is 35Psi; the voltage IS is 5500; the ion source temperature TEM is 500°C; the nebulizer gas GS1 is 55Psi; and the auxiliary gas GS2 is 55Psi.

[0046] The 20 organophosphorus flame retardants determined in this scheme are trimethyl phosphate TMP, triethyl phosphate TEP, tripropyl phosphate TPrP, triisopropyl phosphate TiPP, tri-n-butyl phosphate TnBP, triisobutyl phosphate TiBP, trihexyl phosphate THP, tri-2-ethylhexyl phosphate TEHP, triphenyl phosphate TPEP, tributoxyethyl phosphate TBEP, tri-2-hydroxypropyl phosphate TPHP, triphenylphosphine oxide TPPO, di-2-ethylhexyl phosphate EHDPP, di-1-methylpropyl phosphate MDPP, tri-1-methylpropyl phosphate TMCP, tri-2-tolyl phosphate TOTP, tri-2-chloroethyl phosphate TCEP, tri-2-chloropropyl phosphate TCPP, tri-2,3-dichloropropyl phosphate TDCP, and tri-2,6-dibromophenyl phosphate TDBPP.

[0047] The qualitative and quantitative ion parameter table of these 20 organophosphorus flame retardants is shown in Table 2:

[0048] Table 2 Qualitative and quantitative ion parameters of 20 organophosphorus flame retardants

[0049]

[0050] Specifically, this scheme places the test liquid in liquid chromatography-tandem mass spectrometry for detection. When the retention time of the analyte differs from the retention time of the standard by no more than ±2.5%, the ion pairs of the analyte appear, and the abundance ratio of the qualitative ion pairs is consistent with the abundance ratio of the standard working solution with equivalent concentration, it can be determined that the corresponding analyte to be tested exists in the sample.

[0051] In some embodiments, an external standard method is used to obtain the test contents of 20 organophosphorus flame retardants. Specifically, the standard working solutions of 20 organophosphorus flame retardants are tested under the same liquid chromatography-tandem mass spectrometry conditions and the corresponding standard curves are plotted, and the test contents of the 20 organophosphorus flame retardants to be tested are obtained based on the standard curves.

[0052] The standard curve of this scheme is obtained by weighing a certain amount of each of the 20 organophosphorus flame retardant standards and dissolving them in methanol to prepare a standard stock solution with a concentration of about 1000 mg / L, which is stored at -18°C, and then a certain amount of the standard stock solution is measured in a 10 mL volumetric flask to prepare a mixed standard stock solution with a mass concentration of 20 mg / L, which is stored at -18°C in the dark, and acetonitrile is used to prepare standard working solutions with mass concentrations of 0.5, 1, 2, 5, 10, 20, and 50 μg / L, which are prepared and used immediately. The horizontal axis of the standard curve of this scheme is the substance concentration, and the vertical axis is the response peak area.

[0053] In this scheme, standard working solutions of 20 organophosphorus flame retardants were placed in a liquid chromatography tandem mass spectrometer for testing, and the chromatograms of the 20 organophosphorus flame retardant standards were obtained as shown in the following figure: Figure 2 As shown, this scheme can complete the separation of 20 organophosphorus flame retardants within 15 minutes.

[0054] In addition, the corresponding parameter table of the standard curves of 20 organophosphorus flame retardants is shown in Table 3:

[0055] Table 3 Corresponding parameters of standard curves of 20 organophosphorus flame retardants

[0056]

[0057] The specific formula for calculating the skin migration of organophosphorus flame retardants in this scheme is as follows: ;

[0058] Where X is the skin migration amount of organophosphorus flame retardant, unit is μg / cm 2 ; is the concentration of the organophosphorus flame retardant in the test solution, in μg / L; is the concentration of the organophosphorus flame retardant in the original artificial membrane, in μg / L; V is the volume of the test solution, in L; f is the dilution factor; S is the area of ​​the artificial membrane, in cm 2 .

[0059] It should be noted that the concentration of the organophosphorus flame retardant in the original artificial membrane is obtained by testing the same chromatographic conditions and mass spectrometry conditions of the liquid chromatography tandem mass spectrometer. In the embodiment of this scheme, the concentration of the organophosphorus flame retardant in the original artificial membrane is is 0.

[0060] It should be noted that the concentration of the organophosphorus flame retardant in the test solution is the quotient of the test content of the organophosphorus flame retardant and the volume of the test solution. When the concentration of the organophosphorus flame retardant in the test solution exceeds the linear range of the standard curve, the extract needs to be diluted. If the concentration of the organophosphorus flame retardant in the test solution is within the linear range of the standard curve, the dilution factor is 1.

[0061] Embodiment 1:

[0062] Strat-M TM An artificial membrane was fixed in a dish on the surface of an operating table to simulate human facial skin, a cosmetic sponge containing an organophosphorus flame retardant was fixed on an electric powder puff, the electric powder puff switch was turned on, and the electric powder puff was placed above the artificial membrane to continuously tap the surface of the artificial membrane for 30 seconds. The diameter of the artificial membrane was 2 cm, the rated power of the electric powder puff was 5 W, the rated voltage was 5 V, and the tapping rate was about 3 times per second.

[0063] Remove the artificial membrane from the operating table, cut it into pieces (<5×5mm), put it into a clean centrifuge tube, add 1mL of acetonitrile, cover it and perform ultrasonic extraction for 30min. Take the extract after ultrasonication, filter it with a 0.22 μm nylon filter to obtain the test solution for later use; for target test, use liquid chromatography-tandem mass spectrometry (LC-MS / MS) to perform qualitative and quantitative analysis on the test solution and calculate the skin migration amount.

[0064] The correlation between the skin migration amount obtained in the step of Example 1 and the test content of the organophosphorus flame retardant is shown in the attached figure. Figure 3 As shown, R=0.94, the correlation is good, and the skin migration results obtained by this method are reliable.

[0065] Embodiment 2:

[0066] Validation of Strat-M by matrix spike experimentsTM The accuracy of the method for extracting organophosphorus flame retardants from artificial membranes is determined by the following specific implementation steps:

[0067] Step 1: Take a new artificial membrane and cut it into pieces in a centrifuge tube, add the standard substance at a level of 2.5 mg / kg, add 1 mL of acetonitrile, and perform ultrasonic extraction for 30 min. Take the supernatant and filter it with a 0.22 μm nylon filter to obtain the upper liquid for later use;

[0068] Step 2: using liquid chromatography-tandem mass spectrometry (LC-MS / MS) to conduct qualitative and quantitative analysis on the upper liquid obtained in step 1;

[0069] Three parallel samples (n=3) were set for the sample, and the chromatography, mass spectrometry, qualitative and quantitative analysis conditions in step (2) were the same as those in Example 1, and the average recovery rate data table of each organophosphorus flame retardant was shown in Table 4:

[0070] Table 4 Average recovery rate of organophosphorus flame retardants

[0071]

[0072] As shown in Table 4 , the average recoveries of each OPFRs under this method ranged from 87.75 to 119.68%, and the relative standard deviations ranged from 0.30 to 11.45%.

[0073] Comparative Example 1:

[0074] The difference from Example 1 is that the makeup sponge sample is wetted with water to simulate the process of the organic phosphorus flame retardant migrating to the skin surface during the makeup application process with a wet makeup sponge. The remaining steps are consistent with Example 1. The correlation between the skin migration amount and the content of the analyte is shown in the attached figure. Figure 4 As shown, it can be seen that the correlation R=0.993, which is a good correlation.

[0075] Comparative Example 2:

[0076] Different from Example 1, the migration scenario and process are changed to: 0.1 g of a cosmetic sponge containing an organophosphorus flame retardant is placed in a stoppered test tube, 5 mL of simulated sweat is added to completely immerse the sample, the test tube is sealed and oscillated in a water bath for 60 min (37±5°C) to simulate the process of OPFRs in the cosmetic sponge migrating to the sweat on the skin surface; the extraction process is changed to purifying the simulated sweat after migration through an HLB solid phase extraction column, and the remaining steps are consistent with Example 1.

[0077] The preparation process of simulated sweat is as follows: weigh 0.5 g of L-histidine hydrochloride monohydrate, 5 g of sodium chloride and 2.2 g of disodium hydrogen phosphate dihydrate, dissolve them in distilled water and make up to volume in a 1000 mL volumetric flask, and adjust the pH value of the test solution to 5.5±0.2 with 0.1 mol / L hydrochloric acid solution.

[0078] The purification process of the HLB solid phase extraction column is as follows: 3 mL of methanol and 3 mL of pure water are used to activate the solid phase extraction column in turn, the migration extract is passed through the column, and then the column is rinsed with 3 mL of pure water, the bed is blown dry, and finally eluted with 2 mL of acetonitrile, the eluate is collected and filtered through a 0.22 μm nylon filter head and then tested on the machine.

[0079] The sample testing steps are consistent with those in Example 1. The migration amounts tested in Comparative Example 2 are all lower than the instrument quantification limit. Compared with Example 1 and Comparative Example 1, the lower migration amounts tested by this method will lead to difficulty in quantification and underestimate the exposure risk.

[0080] The present invention is not limited to the above-mentioned optimal implementation mode. Anyone can derive other various forms of products under the inspiration of the present invention. However, no matter what changes are made in the shape or structure, all technical solutions that are the same or similar to those of the present application fall within the protection scope of the present invention.

Claims

1. A method for testing the skin migration of 20 organophosphorus flame retardants in cosmetic sponges, characterized in that: The following steps are involved: A cosmetic sponge containing an organic phosphorus flame retardant is fixed on an electric powder puff device, and the electric powder puff device is used to tap the artificial membrane at a set tapping frequency; The artificial membrane is cut into pieces and then ultrasonically extracted with acetonitrile, and the extract is filtered to obtain the test solution; The test liquid is placed in a liquid chromatography-tandem mass spectrometer to detect the test content of the organophosphorus flame retardant in the artificial membrane; The amount of organophosphorus flame retardant skin migration is calculated based on the test content of the organophosphorus flame retardant in the artificial membrane, the volume of the test liquid, and the area of ​​the artificial membrane; Among them, 20 kinds of organophosphorus flame retardants are trimethyl phosphate TMP, triethyl phosphate TEP, tripropyl phosphate TPrP, triisopropyl phosphate TiPP, tri-n-butyl phosphate TnBP, triisobutyl phosphate TiBP, trihexyl phosphate THP, tri-2-ethylhexyl phosphate TEHP, triphenyl phosphate TPEP, tributoxyethyl phosphate TBEP, tri-2-hydroxypropyl phosphate TPHP, triphenylphosphine oxide TPPO, di-2-ethylhexyl phosphate EHDPP, di-1-methylpropyl phosphate MDPP, tri-1-methylpropyl phosphate TMCP, tri-2-tolyl phosphate TOTP, tri-2-chloroethyl phosphate TCEP, tri-2-chloropropyl phosphate TCPP, tri-2,3-dichloropropyl phosphate TDCP, tri-2,6-dibromophenyl phosphate TDBPP; The chromatographic conditions of the liquid chromatography-tandem mass spectrometry were as follows: a C18 column was used, the column temperature was set at 35-45°C, 0.1% formic acid aqueous solution was used as mobile phase A, methanol mobile phase B was used for gradient elution, the flow rate was 300-400 μL / min, and the injection volume was 1-5 μL; The gradient elution conditions were as follows: at 0.01-2 minutes, the proportion of mobile phase A was set to 25%, and the proportion of mobile phase B was set to 75%; at 2-6 minutes, the proportion of mobile phase A was adjusted to 20%, and the proportion of mobile phase B was adjusted to 80% accordingly; at 6-9 minutes, the proportion of mobile phase A was further reduced to 5%, and the proportion of mobile phase B was increased to 95%; at 9-10 minutes, the proportion of mobile phase A and mobile phase B remained unchanged; at 10-12 minutes, the proportion of mobile phase A was reduced to 0%, and the proportion of mobile phase B was 100%; at 12-13 minutes, mobile phase A was 0%, and mobile phase B was 100%; at 13-15 minutes, the proportion of mobile phase A was restored to the initial 25%, and the proportion of mobile phase B was restored to 75%; at 15.01 minutes, the elution process was stopped; The ion source adopted electrospray ionization positive ion mode ESI+, and the mass spectrometry scanning mode was multiple reaction monitoring MRM mode; the curtain gas CUR was 30~40Psi; the voltage IS was 5200~5700; the ion source temperature TEM was 480~520 ℃; the nebulizer gas GS1 was 52~55Psi; and the auxiliary gas GS2 was 52~55Psi.

2. The method for testing the skin migration of 20 organophosphorus flame retardants in cosmetic sponges according to claim 1, characterized in that: The flapping frequency of the electric powder puff is 2 to 4 times per second, and the flapping time is 20 to 40 seconds.

3. The method for testing the skin migration of 20 organophosphorus flame retardants in cosmetic sponges according to claim 1, characterized in that: The artificial membrane was cut into pieces smaller than 5 mm*5 mm in size and then immersed in 1-3 mL of acetonitrile for 25-40 min of ultrasonic extraction.

4. The method for testing the skin migration of 20 organophosphorus flame retardants in cosmetic sponges according to claim 1, characterized in that: The specific formula for calculating the skin migration of organophosphorus flame retardants is as follows: ; Where X is the skin migration amount of organophosphorus flame retardant, unit is μg / cm 2 ; is the concentration of the organophosphorus flame retardant in the test solution, in μg / L; is the concentration of the organophosphorus flame retardant in the original artificial membrane, in μg / L; V is the volume of the test solution, in L; f is the dilution factor; S is the area of ​​the artificial membrane, in cm 2 .

5. The method for testing the skin migration of 20 organophosphorus flame retardants in cosmetic sponges according to claim 4, characterized in that: When the concentration of the organophosphorus flame retardant in the test solution exceeds the linear range of the standard curve, the extract needs to be diluted. If the concentration of the organophosphorus flame retardant in the test solution is within the linear range of the standard curve, the dilution factor is 1.

6. The method for testing the skin migration of 20 organophosphorus flame retardants in cosmetic sponges according to claim 1, characterized in that: Applied to test 20 organophosphorus flame retardants in cosmetic sponges.

Images