JP2018072100A - Inspection method of resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a qualitative inspection capable of easily determining whether or not a resin material contains phthalate ester as a composition in a short time by accelerating a pretreatment using organic solvent simple in handling.SOLUTION: A solvent-extraction is conducted using the organic solvent that is classified into alcohols and the second petroleum-the fourth petroleum as defined in the fire defense law. In this situation, the organic solvent is heated to the temperature which is higher than a room temperature, and the extraction is accelerated. Next, the organic solvent contained in the extract is concentrated in a short time by promoting its evaporation through bubbling. After that, the concentrate is spectrum-measured by infrared spectroscopy, while the organic solvent is being concentrated or at the end of the concentration. The quantitative determination is conducted as to whether or not a phthalic acid ester is contained as a composition of the resin by confirming whether or not a benzene ring, an alkyl group, and an ester linkage are available on the infrared spectra.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an inspection method for determining whether or not a plasticizer, particularly a phthalate ester, is contained in a resin composition.

  In July 2006, the European RoHS (Restriction of Hazardous Substitutes) Directive that regulates the use of specific hazardous substances for materials used in electronic parts and electrical equipment was enforced. In the European RoHS Directive, in addition to the six substances such as mercury and lead that have already been regulated, it has been decided from July 2019 that four substances such as phthalates will be added. For this reason, when manufacturing and shipping electronic components and electrical equipment, it is necessary to establish a system that guarantees the final product at the component inspection stage because the four phthalate esters do not contain more than the specified concentration. .

  Conventionally proposed methods for analyzing phthalates are high-precision quantitative analysis based on gas chromatography-mass spectrometry (GC-MS method), liquid chromatography-mass spectrometry (LC-MS method), etc. It is. As pretreatment, the following methods have been proposed by the Ministry of Health, Labor and Welfare and the US Consumer Product Safety Commission.

  For example, in the method shown in Non-Patent Document 1, first, a solvent extraction is performed by adding a mixed solution of acetone: hexane = 3: 7 to 1 g of a chopped or crushed sample and allowing to stand at 40 ° C. overnight. Next, after cooling, the mixture is filtered using a filter paper, and the test solution to which acetone is added is analyzed by the GC / MS or GC / FID method.

  In the method disclosed in Non-Patent Document 2, 0.05 g of a sample is first dissolved in tetrahydrofuran (THF), and then hexane is added to precipitate a PVC polymer. Next, after filtering using a polytetrafluoroethylene (PTFE) filter, an internal standard solution (Benzyl Benzoate) is mixed with the THF / hexane solution, and prepared to 1.5 mL with cyclohexane. Finally, it is a procedure of analyzing by GC / MS.

  On the other hand, the amount of resin plasticizer produced in Japan was 220,000 tons in 2015, and the proportion of phthalates in the plasticizer is about 88% of the total. DEHP (Bis (2-ethylhexyl) phthalate), one of the substances scheduled to be regulated under the European RoHS Directive, accounts for about 62% of the total phthalates. Occupy. Phthalates are widely used especially as plasticizers for vinyl chloride resins, and vinyl chloride resins are also the main materials for wire coating materials and hoses, and are widely used in electrical industry products. For this reason, it is necessary to inspect a very large number of members when verifying that they are not contained, and it is very costly and time consuming to analyze all members by the GC-MS method or the LC-MS method. There is a problem.

  In addition, in the above-described GC-MS method and LC-MS method, high-accuracy quantitative analysis is possible, but the initial cost of the analyzer itself is expensive, and its use and maintenance are not only costly, Techniques and expertise for handling analysis devices are required, and there is a problem that analysis takes time.

  Therefore, a method for initial screening of phthalates using infrared spectroscopy has been proposed for these problems. That is, first, from the viewpoint of qualitative determination as to whether or not the phthalate ester itself is contained, a low-cost and simple pretreatment is performed, and then qualitative analysis is performed by infrared spectroscopy. After that, with regard to the contained member, a detailed analysis is performed by the GC-MS method or the LC-MS method regarding whether or not it is a regulated substance and whether or not its contained concentration is within a specified value. is there. Infrared spectroscopic analyzers are cheaper and easier to handle than GC-MS devices and LC-MS devices, and are a general-purpose analysis method for organic material analysis, and are therefore owned by many institutions. Moreover, since it can measure in air | atmosphere, it can measure in a short time. Furthermore, unlike the GC-MS method and the LC-MS method, gas and liquid chemicals used in the analysis are not required, and measurement can be performed with an infrared light source.

  By screening using an infrared spectroscopic analyzer, analysis by GC-MS method or LC-MS method can be performed only on members containing phthalates, so the total cost, Very efficient in terms of time.

  For example, in the method for analyzing phthalates in a resin disclosed in Patent Document 1, first, the plasticizer in the resin is extracted with a solvent at room temperature using alcohol or alkane. By performing extraction at room temperature, the aim is to suppress mixing of the pyrolyzate in the resin into the extract. Next, the extract is dropped onto a water-repellent substrate, naturally dried and concentrated, and finally the dried residue is measured by infrared spectroscopy. Impurities other than the plasticizer are reduced by suppressing the mixing of the thermal decomposition product in the resin during extraction, so that the accuracy of the infrared spectrum obtained by measurement is improved.

  By the way, about 62% of the production of phthalates is DEHP scheduled to be regulated, but the next runner is DINP (Diisononyl phthalate), which is not regulated, accounting for the remaining 38%. In the analysis method of Patent Document 1, since an accurate infrared spectrum that can discriminate between DEHP and DINP is obtained, it is possible to selectively screen only DEHP that is to be regulated.

  Moreover, in the pretreatment method in the analysis of brominated flame retardants in a resin disclosed in Patent Document 2, first, a resin containing a brominated flame retardant is dissolved in an organic solvent at room temperature. Turn into. By dissolving at room temperature, it is possible to remove interference factors and spectrum fluctuation factors due to other additives in the resin. With a solvent such as tetrahydrofuran (THF), toluene, methyl ethyl ketone, etc. as in the examples, solution formation is completed in 10 minutes by natural standing. Next, the solutionized supernatant is dropped on a flat plate to be dried and solidified, and finally the spectrum is measured by infrared spectroscopic analysis or Raman spectroscopic analysis.

  In the preprocessing method of Patent Document 2, interference factors and fluctuations can be suppressed by normal temperature processing, and highly accurate quantitative analysis is possible. The solution solution itself can be further shortened by ultrasonic vibration or centrifugal force, and can be measured as it is set in a spectroscopic analyzer as it is by dropping the solution onto a flat plate without infrared absorption.

  Furthermore, in the spectroscopic analysis method disclosed in Patent Document 3, a sample is first heated at 80 ° C. to 200 ° C. to evaporate substances other than phthalates, and then the sample is heated at 200 ° C. to 400 ° C. Heat to generate phthalate vapors. Then, a sampling plate in which an organic polymer film compatible with phthalates is formed on the reflecting member is exposed to the vapor. Finally, the organic polymer film is irradiated with electromagnetic waves, and the reflection spectrum reflected from the reflecting member is measured.

  According to the analysis method of Patent Document 3, phthalate esters can be adsorbed to polymer membranes by simply exposing them to high-purity steam for 3 minutes. Can be detected.

Japanese Patent Laid-Open No. 2006-45159 JP 2006-322817 A Japanese Patent No. 5732869

Ministry of Health, Labor and Welfare Food Safety 0906 No.4 “Testing Method for Phthalate Esters in Toys” US Consumer Product Safety Commission Test Method: CPSC-CH-C1001-09.3 “Standard Operating Procedure for Determination of Phthalates”

  However, the analysis method disclosed in Patent Document 1 is a method of solvent extraction using alcohol or alkane with respect to a plasticizer in a resin. However, since the temperature at the time of extraction is room temperature, the pace of solvent extraction is slow. Time required increases. For this reason, there is a problem in terms of throughput as a member inspection. In addition, when alkane is used as a solvent, there are also solvents classified as first petroleums, which are more dangerous than alcohol in the Fire Service Act, so there is a problem that the difficulty of handling and management at the manufacturing site increases. Arise.

  In addition, in the pretreatment method disclosed in Patent Document 2, the time required for dissolution at room temperature using an organic solvent is about 10 minutes according to the examples, but the assumed solvents are tetrahydrofuran (THF), toluene. , Methyl ethyl ketone, etc., are high-risk grade solvents classified as the first petroleums stipulated by the Fire Service Act. For this reason, regulations on handling and management are stricter than those of alcohol, and qualification and competence of the handler are required. Therefore, there are problems in that there are high barriers to use and there is a possibility that it cannot be used depending on the work place.

  Furthermore, in the method disclosed in Patent Document 3, phthalate esters are selectively extracted by controlling the sample at a predetermined temperature and heating and evaporating the contents stepwise to be adsorbed on the organic polymer film. According to the technique, the time required for the extraction itself is as short as several minutes, but for the evaporation of phthalates, it is necessary to heat them to a high temperature around 300 ° C. to 400 ° C. above their boiling point. For this reason, the setup time for heating a sample to higher temperature is required, and the power consumption of the equipment by high temperature heating also becomes large. In addition, there is a problem that a heating device or equipment having a temperature range higher than that used in daily life is required, and consideration must be given to preventing accidents such as burns and fire during work.

  The present invention solves the above-mentioned conventional problems and problems, and based on the necessary minimum analysis accuracy assuming a screening operation, on the premise of the use of an inexpensive infrared spectroscopic analysis method and a solvent that is easy to handle, It is an object to provide a balanced inspection method with respect to inspection time, inspection temperature, and operator burden (labor and ability), which are indispensable requirements for application to inspection.

  In order to achieve the above object, the method for inspecting a resin composition according to the present invention uses an organic solvent classified into alcohols and second petroleums to fourth petroleums as defined in the Fire Services Act, The extract obtained by performing solvent extraction at a first temperature higher than room temperature is concentrated using an evaporation promoting means, and the concentrate and / or the residue during and / or at the end of concentration are analyzed by infrared spectroscopy. The possibility of containing phthalates in the resin composition is determined by checking whether or not it has a benzene ring, an alkyl group, and an ester bond.

  According to the present invention, the time required for extraction and concentration is reduced by increasing the temperature during solvent extraction and further concentrating the extract using evaporation promoting means. Therefore, the possibility of containing phthalates can be confirmed by infrared spectroscopic analysis without worrying about resolution. As a result, it is possible to realize a safe and high-throughput inspection with reduced cost and operator burden by suppressing an increase in inspection time while using a low risk grade solvent.

It is a flowchart which shows the procedure regarding the inspection method of Embodiment 1 of this invention. It is a figure which shows typically the process of solvent extraction in the inspection method of Embodiment 1-4 of this invention. It is a figure which shows typically the concentration process of the extract by bubbling transpiration in the inspection method of Embodiment 1 of this invention. It is a graph which shows the temperature dependence of extraction time in the solvent extraction of Embodiment 1-4 of this invention. It is a graph which shows the time shortening effect by the bubbling with respect to concentration time in the concentration process regarding the extract of Embodiment 1 of this invention. It is a graph which shows the spectrum obtained by the infrared spectroscopy about the concentrate or residue obtained by the solvent extraction of Embodiment 1-4 of this invention and a concentration process. It is a figure which shows the molecular structure of DEHP. It is a figure which shows the molecular structure of DINP. It is a flowchart which shows the procedure regarding the inspection method of Embodiment 2 of this invention. It is a figure which shows typically the concentration process of the extract by heating transpiration in the inspection method of Embodiment 2 of this invention. It is a flowchart which shows the procedure regarding the inspection method of Embodiment 3 of this invention. It is a figure which shows typically the mode of adhesion of the resin composition to the container inner surface at the time of bubbling transpiration in the inspection method of Embodiment 3 of this invention. It is a flowchart which shows the procedure regarding the inspection method of Embodiment 4 of this invention. It is a figure which shows typically a mode that the insoluble matter at the time of filtration is isolate | separated in the inspection method of Embodiment 4 of this invention.

  The method for inspecting a resin composition of the present invention includes a step of immersing the resin composition in an alcohol determined by the Fire Service Act and an organic solvent classified into second petroleum to fourth petroleum, and a first higher than room temperature. A step of performing solvent extraction at a temperature, a step of concentrating the extraction liquid using an evaporation promoting means, and a concentrate and / or a residue during and / or at the end of the concentration are analyzed by benzene by infrared spectroscopy. A step of confirming whether or not it has a ring, an alkyl group, and an ester bond, and a step of determining the possibility of containing a phthalate ester in the resin composition.

  As a result, extraction and concentration are accelerated while using a low risk grade solvent, so that the time required for pretreatment can be shortened, and the concentration of phthalates in the extract is concentrated, Even in the case of infrared spectroscopic analysis with a low resolution, it is possible to confirm the possibility of containing phthalates. As a result, it is possible to realize a safe and high-throughput inspection with reduced cost and operator burden.

  Moreover, it is good also as containing 80 mass% or more of ethanol as an organic solvent in that case. Thereby, general industrial alcohol widely used as a solvent (organic solvent), an organic synthetic raw material, a disinfectant, etc. can be used.

  Moreover, it is good also as a temperature below 70 degreeC as 1st temperature at the time of solvent extraction. Thereby, the heating temperature of the organic solvent containing ethanol as a main component is lower than the boiling point of the solvent, and the decrease in the amount of the solvent can be suppressed, so that the extraction amount of the composition can be maximized.

  Moreover, as an evaporation promotion means, it is good also as the method of sending and bubbling a bubble in an extract. As a result, the amount of air bubbles that promote transpiration is almost constant immediately after the start of bubbling, so that the time efficiency is good, and the solvent is evaporated at room temperature, so that a concentration step with a lower environmental load can be realized.

  Further, the evaporation promoting means may be a technique of heating the extract at a second temperature higher than that during solvent extraction. Thereby, it takes time to stabilize the temperature at the start of heating as compared with bubbling, but there is an effect that the transpiration efficiency can be maintained even if the liquid amount is smaller than the size of bubbles.

  Here, it is good also considering the 2nd temperature as the range of 70-200 degreeC. Thereby, since the temperature of an extract becomes more than the boiling point of ethanol, the efficiency of the evaporation of the organic solvent which has ethanol as a main component can be raised.

  In addition, as a concentrate and / or a residue to be subjected to infrared spectroscopy, a substance attached to a side surface in a container being extracted or concentrated may be a confirmation target. As a result, it is possible to shift to infrared spectroscopic analysis when an adhering substance appears in the course of extraction or concentration, so that the pretreatment time can be shortened and the inspection throughput can be improved.

  Further, the concentrate and / or the residue may be further filtered, and a few drops of the filtrate immediately after the start of filtration may be measured by infrared spectroscopy. As a result, insoluble impurities can be removed from the concentrated solution after evaporation of the solvent, and since the filtrate may be a few drops, there is an effect of increasing the concentration while suppressing the influence on the pretreatment time.

(Embodiment 1)
The inspection method of the resin composition in Embodiment 1 of this invention is demonstrated referring drawings. In Embodiment 1, the resin composition is extracted at high temperature using alcohol, the extract is further concentrated by bubbling, and the concentrate is analyzed by infrared spectroscopy, so that the composition contains phthalates. An inspection method (first preprocessing method) for determining whether or not there is a possibility will be described with a specific example.

  FIG. 1 is a flowchart showing a procedure of a resin composition inspection method according to Embodiment 1 of the present invention.

  First, in step S1-1, a sample of the resin composition to be inspected is immersed in alcohol. In FIG. 2, the process of the solvent extraction regarding the composition in the sample in the inspection method of a resin composition is typically shown. In step S1-1, the soft sample piece 1 chopped with a clean scissors is placed in a glass container 3-1, and immersed in an alcohol solution 2-1. Thereafter, the sample glass container 3-1 is sealed with a lid 4 in order to prevent external dust from being mixed into the solution 2-1 and to suppress the decrease of the solution 2-1 due to vaporization.

  In the embodiment, the material of the container 3-1 is made of glass. However, with respect to the portion that comes into contact with the sample and the solution including the lid 4, a material that generates an interfering substance for the resin composition to be analyzed, including metal. There is no problem if it is other than. The shape of the sample 1 may be a bottle or a test tube as long as the sample piece 1 can be taken in and out.

  The total weight of the sample piece 1 and the amount of the solution 2-1 are, for example, 5 g and 10 ml each easy to handle in consideration of the weighing, but the amount of the available sample and the composition in the sample used for analysis It may be determined according to the content, but is not limited to this. In preparing the sample piece 1, a method of scoring as shown in the present embodiment may be used, or a method of pulverizing to a size of 1 mm or less by a pulverizer in order to increase the surface area of the entire sample piece 1 may be used. .

  Next, in step S1-2, the composition is subjected to solvent extraction at a high temperature. As shown in FIG. 2, the solution 2-1 is heated to the same temperature by bringing the container 3-1 enclosing the sample piece 1 into contact with the heating device 5-1 previously heated to 70 ° C. Then, the resin composition is extracted from the sample piece 1 into the solution 2-1.

  FIG. 4 shows a graph of the temperature dependence of the extraction time during solvent extraction. In the graph, the vertical axis represents the weight, the horizontal axis represents the elapsed time, the transition in which the weight of the sample piece 1 decreases from the initial value M1, the transition L1 and the transition L2 for both conditions where the heating temperature is room temperature and 70 ° C. As shown. Here, the weight reduction of the sample piece 1 is regarded as the extraction amount of the resin composition into the solution 2-1.

  This graph shows a tendency that the time required for the predetermined weight reduction is shorter in the transition L2 at 70 ° C. than in the transition L1 under the room temperature condition of the weight. Specifically, as shown in the graph, the time required for transition to a specific weight M2 is T1 (about 220 minutes) at room temperature, and T2 (about 20 minutes) at 70 ° C. The effect is that the time is shortened to about 1/10 by heating.

  Here, as a heating mode of the heating device 5-1, in addition to a method of directly contacting the container 3-1 with the heat source as shown in the present embodiment, indirect by immersion in warm water or using electromagnetic waves. A heating method may be used.

  In addition, in this example, about 10 ml is assumed as the liquid volume of the solution 2-1, but the decrease in the weight of the sample piece 1 is accelerated by increasing the liquid volume, and the time required for solvent extraction T2 can be further shortened. Become. Therefore, the optimum liquid amount may be determined in consideration of the allowable extraction time and the amount of usable alcohol.

  Next, in step S1-3, the extract is bubbled to evaporate the alcohol in the solution. FIG. 3 is a diagram schematically showing an extraction liquid concentration step by bubbling transpiration used in Embodiment 1 of the present invention.

  In the bubbling transpiration, after removing the lid 4 from the container 3-1 after the solvent extraction shown in FIG. 2 and taking out the sample piece 1, the bubbling pipe 6 is introduced into the liquid 2-2 after the extraction. A gas is sent from the pump 7 connected to 6 into the solution 2-2 through the pipe 6. The delivered gas generates bubbles 8 to promote the evaporation of alcohol as an extraction solvent in the solution 2-2, and the extracted resin composition is concentrated in the solution.

  FIG. 5 is a graph showing the effect on concentration time with respect to bubbling during concentration. In the graph, the vertical axis represents the liquid volume, the horizontal axis represents the elapsed time, the transition of the liquid volume of the solution 2-2 from the initial value V1, the transition L3, the transition for both conditions with and without bubbling. Shown as L4.

  Here, the decrease in the liquid volume of the solution 2-2 is regarded as the transpiration amount of the alcohol in the solution 2-2. From this graph, it is shown that the transition amount L4 with bubbling has a shorter time required for a predetermined decrease in the liquid amount than the transition L3 without bubbling. Specifically, as shown in the graph, since the time for transition to a specific liquid volume V2 close to saturation is T3 (about 90 minutes) without bubbling, it is T4 (about 50 minutes) with bubbling. The required time is shortened to near half by bubbling.

  In this embodiment, the atmosphere is used as the gas delivered from the pump 7, but other gases that are chemically inert to the resin and the resin composition may be used.

  In step S1-4, a small amount of the concentrate and / or residue in the glass container 3-1 is sucked up and measured by infrared spectroscopy.

  As a measurement method of infrared spectroscopy, for example, a method of measuring by dropping a small amount of the above concentrate and / or residue on a prism that is in close contact with the sample to be analyzed using ATR (total reflection method) is simple. It is. You may further concentrate the extracted composition by increasing the frequency | count of dripping, drying a dripped material naturally.

  FIG. 6 shows an example of a spectrum obtained by infrared spectroscopic analysis with respect to a concentrate or residue containing phthalates as a composition. The vertical axis indicates the intensity of absorbing infrared light, and the horizontal axis indicates the wave number of infrared light that causes an absorption peak.

  In the next step S1-5, it is confirmed on the infrared spectrum whether a peak is observed at a wave number corresponding to the interatomic vibration of the benzene ring, the alkyl group, and the ester bond. The bonds between atoms that make up the molecule have their own vibrations (stretching vibration and bending vibration). When the molecule is irradiated with infrared light in the mid-infrared region, the vibration between the bonds of each bond It absorbs light having a wave number corresponding to.

  By infrared spectroscopic analysis, the main component of the sample to be analyzed can be estimated by searching the library or comparing it with a known spectrum for the molecule-specific spectrum, which is the sum of the absorption, or the molecule can be determined from the wave number of the absorbed infrared light. It is possible to infer what type of bonds have.

  Note that the composition contained in the sample piece 1 in this example is determined to be DEHP, which is a kind of phthalate ester, by searching the library of the spectrum of FIG. 6 that is the analysis result.

  FIG. 7 and FIG. 8 show the molecular structures of DEHP and DINP as examples of phthalic acid esters used as resin plasticizers. As shown in both figures, phthalates have a molecular structure having a benzene ring structural part G1 and an ester bond structural part G2. In addition to this, DEHP has a structural part G3-1 of an alkyl group which is 2-ethylhexyl, and DINP has a structural part G3-2 of an alkyl group which is isononyl.

Here, wave numbers ν6 and ν7 in the infrared spectrum of FIG. 6 correspond to stretching vibration between carbon atoms (C = C) in the structural part G1 of the benzene ring. The wave numbers ν5 and ν8 represent the interatomic vibration of the structural part G2 of the ester bond, ν5 is the stretching vibration of the carbon-oxygen double bond (C═O), and ν8 is the carbon-oxygen bond (C—O ) Expansion and contraction vibration. Then, the wave number ν1~ν4 represents an atomic vibrations alkyl group structural part G3-1 and G3-2, anti-symmetric stretching vibration of CH ₃ groups and CH ₂ groups ν1 and ν2 constitute each alkyl, .nu.3 and ν4 Corresponds to symmetrical stretching vibrations of the CH ₃ group and the CH ₂ group, respectively.

  In addition, since the phthalate esters have different alkyl group structures depending on the substances, the spectrum shape over wave numbers ν1 to ν4 varies depending on the individual phthalate esters. However, in the wave numbers in ν1 to ν4, depending on some phthalates, there are some wave numbers that do not appear as clear peaks on the spectrum due to low amplitude.

  Finally, in step S1-6, the possibility of containing phthalates is determined. Specifically, when peaks exist in all three wave number groups (ν6, ν7), (ν5, ν8), and (ν1 to ν4) in the infrared spectrum of FIG. It is determined that phthalic acid esters may be contained, and this procedure is terminated.

  After that, regarding quantitative determination of whether it is a substance subject to regulation under the European RoHS directive and whether its concentration is within the specified value, the process moves to a high-precision analysis such as the GC-MS method, and finally a pass / fail determination is made. To do. Alternatively, if no peak is observed in any of the three wavenumber groups (ν6, ν7), (ν5, ν8), and (ν1 to ν4), there is a possibility that phthalates are contained. It is determined that there is no, and the pass determination is made at that time without shifting to high-precision analysis.

  As described above, according to the first embodiment, by using an organic solvent classified into alcohols and second to fourth petroleums, extraction is performed at a temperature higher than room temperature. The resin composition can be extracted in a short time using a solvent.

  Further, by evaporating the extract by bubbling, the solution can be concentrated in a short time to a concentration that can be handled with accuracy of infrared spectroscopic analysis. As described above, it is possible to easily determine whether or not a phthalate ester is contained in the resin sample by inexpensive infrared spectroscopic analysis.

  In this embodiment, the heating temperature at the time of solvent extraction is set to 70 ° C., but it is also possible to select an optimum temperature in consideration of the boiling point of the solvent to be used and the extraction efficiency.

(Embodiment 2)
The inspection method for the resin composition in Embodiment 2 of the present invention will be described with reference to the drawings. In Embodiment 2, the resin composition is extracted at high temperature using alcohol, and the extract is evaporated by heating and concentrated, and the concentrate is analyzed by infrared spectroscopy, so that phthalates as a composition are obtained. An inspection method (second pre-processing method) for determining whether or not there is a possibility of including a specific example will be described with a specific example.

  FIG. 9 is a flowchart showing the procedure of the resin composition inspection method according to the second embodiment of the present invention. Steps S2-1 and S2-2 and S2-4 to S2-6 have the same contents as steps S1-1 and S1-2 and S1-4 to S1-6 of the first embodiment, respectively. The explanation is omitted.

  The difference between the second embodiment and the first embodiment is step S2-3. In step S1-3 of the first embodiment, bubbling is performed to evaporate alcohol from the extract, whereas this embodiment is different from the first embodiment. In step S2-3 of the example, the alcohol for extraction is evaporated by heating the solution to 100 ° C.

  FIG. 10 is a diagram schematically showing an extraction liquid concentration step by heat transpiration used in Embodiment 2 of the present invention. In the heat transpiration, after removing the lid 4 from the container 3-1 where the solvent extraction of FIG. 2 has been completed and taking out the sample piece 1, as shown in FIG. On the other hand, by bringing the container 3-1 into contact, the extracted solution 2-3 is heated to the same temperature and left for a predetermined time. By boiling the alcohol in the solution 2-3, the evaporation of the alcohol is promoted, and the resin composition extracted in step S2-2 is concentrated in the solution.

  Here, as a heating mode of the heating device 5-2, in addition to a method of directly contacting the container 3-1 with a heat source as shown in the present embodiment, indirect by immersion in warm water or using electromagnetic waves. A heating method may be used.

  As described above, in the concentration step in the second embodiment, a method of heating the extract at a temperature higher than that during solvent extraction is employed. For this reason, compared with the bubbling transpiration in the first embodiment, it takes time to stabilize the temperature at the start of heating, but there is an advantage that the transpiration efficiency can be maintained even if the amount of liquid is so small that bubbling cannot be performed.

  In the second embodiment, the temperature at the time of heat concentration is 100 ° C., but it is also possible to select an optimum temperature in consideration of the boiling point of the solvent used and the concentration time.

  Further, the bubbling means described in Embodiment 1 and the heating means of Embodiment 2 may be combined to further shorten the concentration time.

(Embodiment 3)
The inspection method of the resin composition in Embodiment 3 of this invention is demonstrated referring drawings. In Embodiment 3, as a concentrate and / or residue to be subjected to infrared spectroscopy, a substance adhering to the side surface in a container being extracted or concentrated is analyzed by infrared spectroscopy as a confirmation target, thereby obtaining a composition. An inspection method (third pretreatment method) for determining whether or not there is a possibility of containing phthalates will be described with a specific example.

  In FIG. 11, the procedure of the inspection method of the resin composition by Embodiment 3 of this invention is shown with a flowchart. Steps S3-1 to S3-3, S3-5, and S3-6 have the same contents as steps S1-1 to S1-3, S1-5, and S1-6 of the first embodiment. The explanation is omitted.

  The difference between the third embodiment and the first embodiment is step S3-4. In step S1-4 of the first embodiment, the concentrated concentrate and / or residue is subjected to infrared spectroscopy. On the other hand, in step S3-4 of the present embodiment, the substance attached to the side surface in the container being concentrated is subjected to infrared spectroscopy.

  FIG. 12 is a diagram schematically showing how the resin composition adheres to the inner surface of the container during bubbling transpiration in the inspection method according to Embodiment 3 of the present invention. The alcohol is evaporated by the bubbles 8 sent from the pump 7 through the bubbling pipe 6 and generated in the solution 2-2. At the time of transpiration, the deposit 9 may appear on the side surface of the container 3-1 as the liquid volume decreases. In that case, the deposit 9 formed in the course of concentration is collected and infrared spectroscopy is performed. Measure by analytical method.

  As a measuring method of infrared spectroscopy, for example, a method of measuring by dropping the deposit 9 on a prism that is in close contact with a sample to be analyzed using an ATR (total reflection) method is simple. Alternatively, the deposit 9 may be wiped with a metal foil, and the foil itself may be subjected to analysis by an ATR method, a regular reflection method, or the like.

  Phthalates are colorless and transparent oily viscous liquids at room temperature, and as they are concentrated, the residues tend to adhere to the side walls. Accordingly, in step S3-5, on the infrared spectrum shown in FIG. 6, the wave numbers ν6 and ν7 corresponding to the benzene ring, the wave numbers ν5 and ν8 corresponding to the ester bond, and the wave numbers ν1 to ν4 corresponding to the alkyl group. A peak is confirmed and it is determined in step S3-6 that there is a possibility of containing phthalates.

  As described above, in the inspection method shown in the third embodiment, the substance attached to the side surface in the container being concentrated is the object of confirmation. For this reason, compared with the method in the first embodiment, since it is possible to shift to infrared spectroscopic analysis when an adhering substance appears during extraction or concentration, the pretreatment time is shortened and the inspection throughput is improved. There is an advantage that you can.

  In the third embodiment, bubbling transpiration is used in the concentration process shown in S3-3. However, it is also possible to use the heat transpiration described in the second embodiment or a combination of both.

(Embodiment 4)
The inspection method of the resin composition in Embodiment 4 of this invention is demonstrated referring drawings. In Embodiment 4, the concentrate and / or residue may be further filtered, and a few drops of the filtrate immediately after the start of filtration may be analyzed by infrared spectroscopy, which may include phthalates as a composition. An inspection method (fourth pretreatment method) for determining whether or not will be described with a specific example.

  FIG. 13 is a flowchart showing the procedure of the resin composition inspection method according to Embodiment 4 of the present invention. Steps S4-1 to S4-3 and S4-5 to S4-7 have the same contents as steps S1-1 and S1-3 and S1-4 to S1-6 of the first embodiment. The explanation is omitted.

  The difference between the first embodiment and the fourth embodiment is that step S4-4 is newly provided. After the concentration in step S4-3, the filtrate obtained by further filtering the concentrate and / or the residue is infrared. It is to measure by spectroscopy.

  FIG. 14 is a diagram schematically showing how insolubles are separated during filtration in the inspection method according to Embodiment 4 of the present invention. In the filtration, the filter paper 12 is spread on the inner wall of the funnel 11 in advance, and a glass container 3-2 for receiving the filtrate is disposed immediately below the filtrate outlet of the funnel 11. The solution 2-4 in the container 3-1 having completed the solvent concentration is poured onto the filter paper 12 from the spout of the funnel 11. In addition, in the solution 2-4, the other insoluble matter 10 which does not melt | dissolve in a solution shall exist. By filtering with the filter paper 12, the insoluble matter 10 remains on the filter paper, while the filtrate 2-5 is dropped into the container 3-2, and the first few drops are analyzed by infrared spectroscopy.

  Here, natural filtration using gravity applied to the solution 2-4 on the filter paper 12 and in the funnel 11 was shown. However, the pressure reduction filtration by depressurizing the filtrate outlet side of the funnel 11 and the spout side of the funnel 11 were performed. A filtration promoting technique such as pressure filtration by applying pressure, centrifugal filtration using a centrifugal separator, or the like may be employed.

  As described above, in the pretreatment in the fourth embodiment, the concentrate and / or the residue are further filtered, and a few drops of filtrate immediately after the start of filtration are subjected to infrared spectroscopy. For this reason, insoluble impurities can be removed from the concentrated solution after evaporation of the solvent, and since the filtrate may be a few drops, there is an advantage that the concentration increases while suppressing the influence on the pretreatment time.

  In the fourth embodiment, bubbling transpiration is used in the concentration process shown in S4-3. However, the heat transpiration described in the second embodiment, or a combination of both can be used.

  The inspection method of the present invention has been described in detail in the first to fourth embodiments. In each of the embodiments, as the solvent extraction steps S1-2, S2-2, S3-2, and S4-2, a technique for promoting extraction by heating the sample at a high temperature is shown. As another method for promoting extraction, as in this case, the sample piece is indirectly pressurized by using the internal pressure increase caused by heating the container sealed with the lid, or the sample piece at the time of solvent extraction is used. A method of applying a constant or intermittent pressure to the sample piece, such as directly pressing the sample piece with a jig, is also conceivable.

  In addition, by repeating these inspection methods on a daily basis, it is possible to empirically contain phthalates from the properties and hues of concentrates and / or residues without using infrared spectroscopy. It would also be possible to estimate sex.

  The method for inspecting a resin composition of the present invention can ensure work safety, reduce equipment costs, and shorten the time required for pretreatment in analysis pretreatment of phthalates that are plasticizers in a resin, The present invention can be widely applied to the field where the initial screening of the resin composition in the inspection is easily performed.

1 Sample piece 2-1, 2-2, 2-3, 2-4, 2-5 Solution of resin composition in each pretreatment step 3-1, 3-2 Glass container used in pretreatment step 4 Lids 5-1, 5-2 Heating device 6 Bubbling pipe 7 Pump 8 Air bubbles 9 Deposits 10 Insoluble matter 11 Funnel 12 Filter paper S1-1 to S1-6 Inspection steps S2-1 to S2 in the first embodiment of the present invention -6 Inspection Steps in Embodiment 2 of the Present Invention S3-1 to S3-6 Inspection Steps in Embodiment 3 of the Present Invention S4-1 to S4-7 Inspection Steps in Embodiment 4 of the Present Invention M1, M2 Resin Sample weight before and after composition extraction L1, L2 Transition of sample weight under conditions of room temperature and high temperature T1, T2 Time required for sample weight to decrease to M2 under conditions of room temperature and high temperature V1, V2 Solution Amount of solution before and after shrinkage L3, L4 No bubbling, transition of solution amount in each condition with T3, T4 No bubbling, time required for solution to decrease to V2 under each condition ν1 to ν4 Infrared spectroscopy spectrum Wavenumber corresponding to interatomic vibration of alkyl group in ν6, ν7 Wavenumber corresponding to interatomic vibration of benzene ring in infrared spectrum ν5, ν8 Wavenumber corresponding to interatomic vibration of ester bond in infrared spectrum G1 Phthalic acid Structural part of benzene ring in esters G2 Structural part of ester bond in phthalates G3-1 G3-2 Structural part of alkyl group in phthalates

Claims (8)

An inspection method for a resin composition,
Using the resin composition, an organic solvent classified into alcohols and second petroleums to fourth petroleums stipulated in the Fire Service Act,
Concentrate using an evaporation promoting means for the extract obtained when solvent extraction is performed at a first temperature higher than room temperature,
By confirming whether the concentrate and / or the residue during and / or at the end of the concentration have a benzene ring, an alkyl group, and an ester bond by infrared spectroscopy,
A method for inspecting a resin composition, comprising determining the possibility of containing phthalates. The inspection method according to claim 1, wherein the organic solvent contains 80% by mass or more of ethanol. The inspection method according to claim 1, wherein the first temperature is a temperature of 70 ° C. or less. The said evaporation promotion means is an inspection method of any one of Claims 1-3 which bubbles the said extract. The said evaporation promotion means is an inspection method of any one of Claims 1-3 which heats the said extract at 2nd temperature higher than said 1st temperature. The inspection method according to claim 5, wherein the second temperature is in a range of 70 to 200 ° C. The said concentrate and / or residue are the substances adhering to the side surface in the said container, when the said solvent extraction is performed within a predetermined | prescribed container, The any one of Claims 1-3 characterized by the above-mentioned. Inspection method. The inspection method according to any one of claims 1 to 3, wherein the concentrate and / or the residue are further filtered, and a few drops of the filtrate immediately after the start of filtration are measured by infrared spectroscopy.

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