CN112011125B - Polypropylene film standard sample with plasticizer migration value and preparation method thereof - Google Patents
Polypropylene film standard sample with plasticizer migration value and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polypropylene film manufacturing, and discloses a polypropylene film standard sample with a plasticizer migration value and a manufacturing method thereof. Uniformly mixing a plasticizer and part of polypropylene resin raw materials, and extruding to prepare master batches; and then mixing the master batch with the rest polypropylene resin raw materials according to a set proportion, blowing a film to obtain a polypropylene film, and performing series treatment on the film to obtain a standard sample. The prepared polypropylene standard sample has good uniformity and stability, and can be used for comparing plasticizer migration value detection data in a polypropylene film between laboratories, verifying accuracy of a method, calibrating a test instrument and controlling and checking quality of a test result.
Description
Technical Field
The invention relates to the technical field of polypropylene films, in particular to a polypropylene film standard sample with a plasticizer migration value.
Background
Polypropylene (PP) is a semi-rigid plastic that can be widely used to make food packaging bags or films. In order to prolong the service life and improve the physical properties, small molecule processing aids are often used in the production of plastic packages. In 20 types of available processing aids, the standard for using additives for food containers and packaging materials (GB 9685-2016) issued in 2016 in China stipulates that the maximum allowable usage amount of the plasticizer is up to 5-50%, which is far higher than that of other additives by 0.1-10%, and the plasticizer has various chemical varieties, and more than 200 types of plasticizers can be used for commercial production. Among them, the phthalate plasticizer is most widely used and the amount of the phthalate plasticizer is the largest, and accounts for about 80% of the total amount of the plasticizer. Adipate plasticizers are also a common plasticizer and are often used in combination with phthalates in the food packaging industry, but plasticizers run the risk of migration from the packaging material to the food product upon prolonged contact with the food product. For this reason, regulations are made in various countries of the european union, the united states, china, japan, and the like to limit the use of certain plasticizers in food contact materials, and the maximum amount of usable plasticizers and a Specific Migration Limit (SML) are specified.
Due to the strict requirements of countries in the world on the plasticizer in the food contact material, many laboratories have conducted research on migration risks of food packaging materials and have conducted work for detecting the migration amount of the plasticizer in the plastic packaging materials for food. However, the accuracy of the method is verified by adopting an additive recovery rate method no matter the detection standard or the internal quality control of a laboratory. The difference between the migration behaviors of the plasticizer added into the migration solution and the plasticizer in the plastic is large, and the verification mode is not good enough; the level of each laboratory and laboratory personnel is uneven and there is no good quality control means, resulting in lack of quality control inside the laboratory and lack of comparability of measurements between laboratories. At the same time, the migration behaviour in different simulants and also in foodstuffs is not sufficiently clear, since no plastic sample was identified for the plasticizer migration value. Therefore, the preparation of the plastic food packaging standard substance which has a good guarantee effect on the accuracy, consistency and value traceability of the detection result is of great significance.
At present, although most experiments in China have the capability of detecting the plasticizer in the food package, the national does not have the standard sample/substance related to the plasticizer in the plastic food package, the types of the standard sample/substance in the aspect are few internationally, and only the standard sample/substance with element content or the standard sample/substance of the total transferee in a certain plastic material is reported in the standard substance library provided by main standard substance development and supply organizations in the world such as an international standard substance information library, a National Institute of Standards and Technology (NIST), an European Union standard substance information platform (IRMM), a British analytical chemistry Standard test Laboratory (LGC) and the like, and the standard sample/substance related to the organic plastic additive is not reported yet.
Disclosure of Invention
The invention aims to provide a polypropylene film standard sample with a plasticizer migration value, and the polypropylene film standard sample has good uniformity and stability.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a polypropylene film standard sample with a plasticizer migration value, which comprises the following steps: uniformly mixing a plasticizer with part of polypropylene resin raw materials, and extruding to prepare master batches; and then mixing the master batch with the rest polypropylene resin raw materials according to a set proportion, blowing a film to obtain a polypropylene film, and performing series treatment on the film to obtain a standard sample.
In an alternative embodiment, the plasticizer is added in an amount of 0.1% to 5%.
As an alternative embodiment, the plasticizer is a phthalate-based plasticizer or an adipate-based plasticizer.
Further, the phthalate plasticizer includes dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate and diisobutyl phthalate.
Further, the adipate plasticizer comprises di (2-ethyl) adipate, dimethyl adipate, diisobutyl adipate and di-n-butyl adipate.
As an alternative embodiment, the plasticizer is mixed with half of the weight of the polypropylene resin raw material for granulation, and then the prepared master batch is mixed with the other half of the polypropylene resin raw material for film blowing.
Further, the plasticizer and the polypropylene resin raw material are mixed according to the weight ratio of 1; and then, fully mixing the master batch and the polypropylene resin raw material according to the weight ratio of 1.
As an alternative, the series of treatments is to cut the front, back and both side portions of the film, taking the middle polypropylene film as the polypropylene standard.
As an alternative embodiment, the standard sample is subpackaged in aluminum foil bags and sealed for storage.
The invention also comprises a polypropylene film standard sample prepared by any one method.
As an alternative embodiment, the migration amount of the standard sample of the polypropylene film is determined under the following conditions: the food simulant adopts isooctane solution as the food simulant, and the ratio of the volume to the area of the sample is 100mL:0.6dm 2 The test is carried out in a full immersion contact mode at the immersion temperature of 60 ℃ and the migration time is 4h.
As an alternative embodiment, the polypropylene film standard sample is subjected to statistical analysis of the uniformity of the standard sample by one-way analysis of variance.
The technical scheme of the invention has the following beneficial effects:
the polypropylene film standard sample with the plasticizer migration value is prepared by uniformly mixing the plasticizer and part of polypropylene resin raw materials, and extruding to prepare master batches; and then mixing the master batch with the rest polypropylene resin raw materials according to a set proportion, blowing a film to obtain a polypropylene film, and performing series treatment on the film to obtain a standard sample. Through inspection, the polypropylene standard sample prepared by the invention has good uniformity and stability, and can be used for comparison of plasticizer migration value detection data in a polypropylene film between laboratories, accuracy of a verification method, calibration of a test instrument and quality control and assessment of a test result. The invention has low cost of raw materials and simple preparation method, and the obtained standard sample is a material standard sample, uniform and stable and is easy to store.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Polypropylene film standards containing 1% dibutyl phthalate (DBP)
The PP raw material and dibutyl phthalate (DBP) are mixed according to the weight ratio of 9. And then, fully mixing the master batch and the PP raw material according to the ratio of 1. Two meters before and after the produced PP film were discarded, while the rolled PP film was cut 5cm each on both sides, with the middle PP film being a standard sample (about 20cm wide). Then, the PP film was cut in a unit of 60cm in length, and was subpackaged in aluminum foil bags, and stored in a sealed manner, with a total of 200 parts of each PP film.
Example 2
Polypropylene film standard sample containing 1% diisobutyl phthalate (DIBP)
Firstly, mixing a PP raw material and diisobutyl phthalate (DIBP) according to the weight ratio of 9. And then, fully mixing the master batch and the PP raw material by a blowing machine according to the ratio of 1. Two meters before and after the produced PP film were discarded, while the rolled PP film was cut 5cm each on both sides, with the middle PP film being a standard sample (about 20cm wide). Then, the PP film was cut in a unit of 60cm in length, and was subpackaged in aluminum foil bags, and stored in a sealed manner, with a total of 200 parts of each PP film.
Example 3
Polypropylene film standards containing 1% Di (2-ethyl) hexyl adipate (DEHA)
Firstly, mixing a PP raw material and di (2-ethyl) hexyl adipate (DEHA) according to the weight ratio of 9. And then, fully mixing the master batch and the PP raw material according to the ratio of 1. Two meters before and after the produced PP film were discarded, while the rolled PP film was cut 5cm each on both sides, with the middle PP film being a standard sample (about 20cm wide). Then, the PP film was cut in a unit of 60cm in length, and was subpackaged in aluminum foil bags, and stored in a sealed manner, with a total of 200 parts of each PP film.
Example 4
Polypropylene film standards containing 4% dioctyl phthalate (DEHP)
The PP raw material and dioctyl phthalate (DEHP) are mixed according to the weight ratio of 4. And then, fully mixing the master batch and the PP raw material by a blowing machine in a ratio of 1. Three meters before and after the produced PP film was discarded, while the rolled PP film was cut 5cm on both sides, the middle PP film being a standard sample (about 20cm wide). Then, the PP film was cut in a unit of 60cm in length, and was subpackaged in aluminum foil bags, and stored in a sealed manner, with a total of 200 parts of each PP film.
Example 5
Polypropylene film standards containing 0.5% dimethyl adipate (DMA)
The PP raw material and dimethyl adipate (DMA) are mixed according to the weight ratio of 9. And then, fully mixing the master batch and the PP raw material by a blowing machine in the proportion of 1. The front and back two meters of the produced PP film were discarded while the rolled PP film was cut 5cm on both sides, the middle PP film being a standard sample (about 20cm wide). Then, the PP film was cut in a unit of 60cm in length, and was subpackaged in aluminum foil bags, and stored in a sealed manner, with a total of 200 parts of each PP film.
Example 6
Selection of migration conditions of polypropylene film standard sample
Research on migration rules is carried out according to the method of 'full immersion exposure in thermostatic oven, thermostat or refrigerator' specified in GB/T23296.1-2009The food simulant adopts isooctane solution as the food simulant, and the ratio of the volume to the area of the sample is 100mL:0.6dm 2 The test is carried out in a full immersion contact mode at the immersion temperature of 60 ℃ and the migration time is 4h.
Under the condition, the prepared sample migration test obtains ideal results and also accords with relevant regulations at home and abroad, so the migration fixed value is carried out by adopting the above condition. The experiment is determined according to GB 31604.30-2016 (national food safety standard) determination and determination of transfer amount of phthalate, GB 31604.28-2016 (national food safety standard) determination and determination of transfer amount of di (2-ethyl) hexyl adipate, and SN/T2826-2011 (gas chromatography-mass spectrometry) determination of adipate plasticizer in food contact material high molecular material food simulants.
Example 7
Polypropylene film standard sample uniformity test
The uniformity evaluation methods of the samples are various, the analysis of variance for evaluating the uniformity of the standard substances is generally adopted for the development of the standard substances, and the single-factor analysis of variance is found to be suitable for the statistical analysis of the uniformity of the standard samples along with the development of the subjects and the release of related standard methods.
The single-factor analysis of variance is described in JJG 1006-4994 "Primary Standard substance technical Specification", JJF 1343-2012 "general requirements for Standard substance definite value and statistical principles", and CNAS-GL003:2018, the 'guide basis for evaluating uniformity of samples for capability verification' has certain regulations, and whether the measured values of all groups have system errors is judged by the variance between groups and the variance in the groups, and if the comparison value of the variance between the groups and the variance in the groups is smaller than the critical value of the statistical test, the samples are considered to be uniform.
Calculate mean within group:
overall average value:
statistics:
in the formula:
i.e. the sum of the squares of the differences between the groups;
degree of freedom: f. of 1 ＝m-1，f 2 ＝m(n-1)
Where m is the number of samples taken and n is the number of measurements made for each sample. The criticality table is looked up according to the significance level α (typically 0.05). The test result is subjected to uniformity test and evaluation by adopting a single-factor variance analysis method (F test method), and F is obtained by looking up an F distribution table Critical value of ，F＜F Critical value The sample uniformity was considered satisfactory.
Taking the example of DBP in example 1, after completion of sample aliquoting, 15 specimens were drawn from each set of prepared specimens in random order for homogeneity testing, with randomly drawn specimens numbered from 1 to 15. Randomly drawing each unit and repeating the determination 3 times (within group), wherein the determination sequence is 1,2,3, \ 8230; \ 8230; 15;15,14,13, \8230;, 1;1,2,3, \ 8230 \ 8230and 15. The test method adopts a method specified in national standard GB 31604.30-2016 (determination of phthalate of food contact materials and products) and determination of migration quantity) to extract, and adopts a gas chromatography-mass spectrometer (GC-MS) to determine. And analyzing and checking the measurement data by using a one-factor variance method to judge whether the uniformity of the standard substance is qualified. As can be seen from Table 1, the F value is 1.85 less than F 0.05,(14,30) The critical value of 2.04 indicates that the sample uniformity meets the requirements of the standard sample.
TABLE 1 results of homogeneity experiments (mg/dm) of DBP in PP standards 2 )
Example 8
Polypropylene film standard sample stability test
GB/T15000.3-2008 states that the standard sample rating requires consideration of two types: long term stability of the material and short term stability of the material. Taking the example of DBP in the PP sample of example 1, the sample was prepared and sealed in a vacuum aluminum foil bag to test the stability.
1 short term stability test
In order to test the stability of the standard substance in transportation, the stability test samples are divided into normal temperature and high temperature, and the high temperature group is placed in a thermostatic chamber at 37 ℃ for one week to simulate the summer transportation environment. The stability of the standard material was verified by the t-test method, and the results are shown in Table 2.
2 Long term stability test
The samples were packed in compound tinfoil bags according to their storage and transport conditions and tested for stability at room temperature for 2 years. At 3 months, 6 months, 10 months, 16 months, 19 months, 24 months during the test period, samples were taken for testing. And (3) respectively carrying out T test and trend analysis to evaluate the stability of the standard substance according to the general principle and statistical method of standard sample fixed value of GB/T15000.3-2008 standard sample work guide (3).
Calculate statistic S d And t is in the formula
s 1 、n 1 Respectively the average value, the standard deviation and the measurement times of the in-bottle measurement results,
s 2 、n 2 respectively the average value, the standard deviation and the measurement times of the inter-bottle measurement results; calculating the value of statistic t, if t is less than t Critical value Then can confirmNo significant change was observed in the standard substance.
The judgment method adopts a straight line as an empirical model, and the slope is calculated by the following formula:
Intercept calculation formula:
the standard deviation of the points on the straight line is calculated by the formula:
slope-related uncertainty calculation formula:
values derived from student distribution t-factors with degree of confidence n-2 and p =0.95 (95% confidence level) were found, both t values being less than the cutoff value.
Then compare | b 1 I and t 0.05,n-2 ·s(b 1 ) If the magnitude is less than the predetermined value, the slope is not significant, indicating that no instability is observed. Stability test regression equations were used to check the significance of the stability trend. From the above table data, the regression equation for the average value (y) of each time segment versus the stability test time interval (x) is:
y＝3.625+0.00082x
standard deviation s =0.146, slope of the regression equationb 1 Has a standard deviation of s (b) 1 ) =0.00795, degree of freedom v = n-2=4, selectivity level 0.05,t 0.05,4 ＝2.78，t0.05,4×s(b 1 ) =0.0221, due to | b 1 |＜t 0.05,4 ×s(b 1 ) The standard substance was considered stable during the test.
TABLE 2 stability analysis of DBP in PP
Example 9
1 valuing method
According to the general principle and statistical method of standard sample valuing of GB/T15000.3-2008 standard sample work guide (3), the determination of characteristic values of standard samples has various schemes, but the optimal scheme is the collaborative valuing of a plurality of laboratories. Therefore, 3 samples with consistent homogeneity and stability were selected and 15 laboratories were organized for synergy. All participating laboratories were those developing food contact materials. Referring to GB 31604.30-2016, each sample is subjected to 2 independent tests, each independent test is performed for 2 times in parallel, and the test result is reported to 3 bits after decimal point. The characteristic values of the standard samples are obtained through sample distribution, detection, result feedback and data statistical analysis, and the summarized data are shown in table 3.
TABLE 3 results of collaborative laboratory valuation
Note: the underline data is abnormal value removed by accuracy inspection such as Cokelen
2 data summarization analysis
The JJF 1006-1994 first-level standard substance technical specification states that the data of the cooperative setting value needs to be judged to be correct by means of normality detection, abnormal value detection, equal-precision detection and the like.
2.1 normalization of data
When the data volume N is more than or equal to 8 in the statistical processing and the interpretation normality test of GB/T4882-2001 data, a bias state (b) s ) And peak state (b) k ) Combined test method. The present standards had a collaborative rating of 15, with four data per parameter, so there were 60 data per parameter.
Summarize all raw data, use b s And b k And (4) detecting the normal distribution of the test sample by a joint test method, and removing abnormal measured values.
The detection method comprises the following steps: the raw data were all collected and the following parameters were calculated
Wherein: m is the number of laboratories; n-number of measurements per laboratory
The statistic of the test is determined by the above equation to be a pair | b s I and b k Under the assumption of a positive zero, at | b s I and b k Can draw a region around a point (0, 3) in the coordinate axis system of (1), the point (| b) s |，b k ) The probability of falling within this region is p and the contours of these regions are given in GB/T4882-2001 in fig. 9a (p = 0.95) and fig. 9b (p = 0.99).
Calculated | b according to the above method s I and b k See attached table, compare p =0.95 with the profile (0.75, ± 4.95) of fig. 9a in GB/T4882-2001, see inspectionTest whether the result falls within the normal range. Verified, there is a set of points (| b) of data s |，b k ) Falling outside the contour. Two values of the set of numbers are found to be abnormal values in the following Gibbs test abnormal value elimination test, and | b is calculated after the abnormal values are eliminated s I and b k The point at this time was found to fall within the normal range contour. Obtaining a normal test conclusion: after the abnormal values are eliminated, the data of the cooperative constant values are in normal distribution.
2.2 outlier test
According to GB/T4883-2008 'statistical treatment of data and judgment and treatment for analyzing outlier of normal sample', the Grubbs test method is adopted to detect whether abnormal values exist in data or not
Upper case:
lower side situation
Wherein
And s is the sample mean and the sample standard deviation; the detection level α is determined and G is found in Table A2 of GB/T4883-2008 1-α (n) when G n Or G n '＞G 1-α (n), judging x (n) Or x (1) Is an outlier, otherwise x is not found (n) Or x (1) Is an outlier.
2.3 Cokronen-like precision test
After removing abnormal values, the average value and standard deviation of each laboratory are calculated for the data which accord with normal distribution, the Cochran (Cochran) test is carried out on the maximum value of the standard deviation, and a statistical value C is calculated.
According to the significance level and the detection times, finding out a Cochran test critical value C, if C is Experimental values ＞C (0.01,m,n) Then S is max Should be rejected for suspicious value, if C Experimental values ＜C (0.05,m,n) That is, the measurement values of m laboratories are equal-precision measurement values. If C (0.05,m,n) ＜C Experimental values ＜C (0.01,m,n) Care should be taken to avoid such problems.
The specific situation of rejecting abnormal values through normal distribution test, grabbs abnormal value test, koclen precision test and the like of the cooperative fixed value data is shown in an attached table 4.
TABLE 4 results of the test for the accuracy of normal distribution, grubbs outlier and Koclen
Note: verification of raw data for underlined data
3 uncertainty analysis
3.1 evaluation principles
The uncertainty of the standard sample was evaluated according to JJF1059-1999 assessment and presentation of uncertainty of measurement, JJF 1006-1994 technical Specification of first class Standard substance and GB/T15000.3-2008 general principles and statistical methods for rating Standard sample according to the Standard sample's operating guide (3). The mean value of the mean values of the respective constant value units was used as a standard value.
3.2 measurement uncertainty calculation
The calculation formula of the uncertainty of the A-type synthesis standard is as follows:
in the formula: u. of A A synthetic standard uncertainty for the characteristic value; u. of char Standard uncertainty due to fixed value measurements; u. of bb Standard uncertainty due to sample (non) uniformity; u. u lts Standard uncertainty due to long term (non-) stability; u. of sts Is the standard uncertainty due to short term (non-) stability. The samples were stable for a short period of time, which caused negligible standard uncertainty.
3.3 uncertain calculation of Synthesis criteria
The standard samples were evaluated for standard uncertainty with the arithmetic mean of 15 cooperating rating laboratories as the best estimate (consensus) and the class a uncertainty as the mean. Using extended uncertainty U = kU r Representing the final uncertainty (including the factor k = 2). Uncertain reduction was performed by the round-trip method, and the standard values and extended uncertainties of the three standard samples are shown in Table 3.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A preparation method of a polypropylene film standard sample with a plasticizer migration value is characterized in that a PP raw material and dibutyl phthalate are mixed according to a weight ratio of 9; then, fully mixing the master batch and the PP raw material by a blow molding machine according to the ratio of 1;
or mixing the PP raw material and the diisobutyl phthalate in a weight ratio of 9; then, fully mixing the master batch and the PP raw material by a blowing machine according to the ratio of 1;
or mixing the PP raw material and di (2-ethyl) hexyl adipate in a weight ratio of 9; and then, fully mixing the master batch and the PP raw material according to the ratio of 1.
2. The method of claim 1, wherein the front, back and side portions of the PP film are cut, and the middle polypropylene film is taken as a polypropylene standard sample.
3. A standard sample of polypropylene film prepared by the method of claim 1 or 2.
4. The polypropylene film standard according to claim 3, wherein the migration amount of the polypropylene film standard is measured under the following conditions: the food simulant adopts isooctane solution as the food simulant, and the ratio of the volume to the area of the sample is 100mL:0.6dm 2 The test is carried out in a full immersion contact mode at the immersion temperature of 60 ℃ and the migration time is 4h.
5. The polypropylene film standard according to claim 3, wherein the polypropylene film standard is subjected to statistical analysis of standard uniformity by one-way ANOVA.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344624A (en) * | 2011-06-30 | 2012-02-08 | 福建出入境检验检疫局检验检疫技术中心 | Preparation method of standard sample for testing phthalic ester plasticizer |
| CN103900879A (en) * | 2014-03-24 | 2014-07-02 | 河北出入境检验检疫局检验检疫技术中心 | Preparation method of standard sample for specific migration quantity detection on restricted substances in polyethylene film |
| CN105647046A (en) * | 2016-04-11 | 2016-06-08 | 北京市理化分析测试中心 | Preparation method of phenolic-antioxidant-containing positive control substance of food contact plastics |
| CN106751217A (en) * | 2016-12-28 | 2017-05-31 | 广东出入境检验检疫局检验检疫技术中心 | A kind of preparation method of plasticizer-containing plastic cement standard sample |
| CN106832881A (en) * | 2017-01-16 | 2017-06-13 | 浙江省计量科学研究院 | Phthalic ester plasticizer and phosphorus flame retardant standard sample and sample preparation methods in polyurethane |
| KR20190065772A (en) * | 2017-12-04 | 2019-06-12 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising the same |
-
2020
- 2020-09-07 CN CN202010929216.1A patent/CN112011125B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344624A (en) * | 2011-06-30 | 2012-02-08 | 福建出入境检验检疫局检验检疫技术中心 | Preparation method of standard sample for testing phthalic ester plasticizer |
| CN103900879A (en) * | 2014-03-24 | 2014-07-02 | 河北出入境检验检疫局检验检疫技术中心 | Preparation method of standard sample for specific migration quantity detection on restricted substances in polyethylene film |
| CN105647046A (en) * | 2016-04-11 | 2016-06-08 | 北京市理化分析测试中心 | Preparation method of phenolic-antioxidant-containing positive control substance of food contact plastics |
| CN106751217A (en) * | 2016-12-28 | 2017-05-31 | 广东出入境检验检疫局检验检疫技术中心 | A kind of preparation method of plasticizer-containing plastic cement standard sample |
| CN106832881A (en) * | 2017-01-16 | 2017-06-13 | 浙江省计量科学研究院 | Phthalic ester plasticizer and phosphorus flame retardant standard sample and sample preparation methods in polyurethane |
| KR20190065772A (en) * | 2017-12-04 | 2019-06-12 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising the same |
Non-Patent Citations (1)
| Title |
|---|
| 塑料包装材料DBP、DPP在油脂中的迁移规律;王楠等;《浙江树人大学学报(自然科学版)》;20130615;第13卷(第02期);第36-40页 * |
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