JP4389078B2 - Method for measuring organic volatiles in organic materials - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for measuring an organic volatile matter of an organic material, and more particularly to a method suitable for measuring a highly adsorbing organic compound that volatilizes in a trace amount from an organic material.
[0002]
[Prior art]
There is a problem in that an organic compound present in a clean room atmosphere is adsorbed on the surface of the semiconductor wafer and affects its electrical characteristics. Although organic compounds are generated from various organic materials, a typical example is dioctylphthalic acid (DOP). Dioctyl phthalic acid is often used as a plastic additive in plastic materials. Dioctyl phthalic acid has a boiling point of 360 ° C. and is slightly volatile at room temperature. For this reason, dioctylphthalic acid is usually contained in a trace amount of 0.1 to 1 ng / L in a clean room atmosphere. Therefore, it is necessary to evaluate those organic compounds that adsorb on the wafer surface.
[0003]
Currently, volatile organic compounds from plastic materials are measured using the method described in the “Measurement Guidelines for Molecular Pollutants Generated from Cleanroom Constituent Materials (draft)” of the Japan Air Cleaners Association. A schematic diagram thereof is shown in FIG. In this measurement, the organic compound that volatilizes from the test piece is collected in the collection tube in front of the suction pump after adjusting the measurement time with an integrating flow meter in an atmosphere where the airflow flows in a certain direction by the suction pump. It is a method to do. First, a test piece 1 such as a plastic material from which an organic compound to be measured volatilizes is placed in a chamber 2. The chamber 2 is made of a stainless steel or glass container. An inert gas such as clean air or nitrogen gas is injected from a pipe passing through the inlet in the upper part of the chamber 2, and an organic compound that volatilizes from the test piece is carried on an air stream through a pipe connected to the outlet in the upper part of the chamber 2. , And collected in a collection tube such as the impinger 3 or the collection agent 4. After the collection, the type and amount of the volatile organic compound are measured on the collection tube by a thermal desorption gas chromatograph.
[0004]
Patent Document 1 has a structure that uses an adsorption tube container that can be directly attached to a mass spectrometer of a gas chromatograph, and performs thermal desorption by attaching the adsorption tube container to the mass spectrometer while containing a test piece that adsorbs contaminants. The pollution material and the amount of pollutant are measured to evaluate the degree of contamination at the location to be measured.
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 2001-264295
[Problems to be solved by the invention]
However, the problem of the measurement method guideline is that organic compounds generated from plastic materials that have strong adsorptivity are adsorbed on the inside of the chamber or the inner wall of the pipe through which the airflow flows, and cannot reach the collection tube. For this reason, it is difficult to accurately measure the type and amount of the generated organic compound.
[0007]
The objective of this invention is providing the organic volatile matter measuring method of an organic material which can measure accurately also with respect to the organic compound with strong adsorptivity volatilized from an organic material.
[0008]
[Means for Solving the Problems]
In order to achieve the above object, a method for measuring organic volatiles of a polymer organic material according to the present invention inserts a sample of an organic material between an inlet of a volatilization container previously filled with a collecting agent and the collecting agent. Then, after collecting the volatile organic compound that volatilizes from the organic material, by attaching the volatile container with the volatile organic compound attached to the mass spectrometer, the volatile container and the collecting agent are included. wherein an organic volatiles measuring method of the organic material of the measurement of volatile organic compounds, said volatile container fractionated into a suction unit containing a volatile portion and the collection agent, the volatile portion and the discharge port of the suction portion Directly connecting each other, storing the sample of the organic material in the volatile part, volatilizing the volatile organic compound, collecting the volatile organic compound volatilized from the organic material by the adsorption part in the subsequent stage, and Part and said And a wearing portion was measured by mounting the mass spectrometer separately, and characterized in that the total value and analytical values of the organic compound.
Further, after the volatile container previously filled with the organic compound collector is cleaned by a heat heating method, a sample of the organic material is inserted between the inlet of the volatile container and the collector, By collecting the volatile organic compound that volatilizes from the organic material in the volatile container and attaching the volatile organic compound attached to the mass spectrometer together with the volatile container to which the volatile organic compound is attached, in a form including the volatile container and the collector. wherein an organic volatiles measuring method of the organic material of the measurement of volatile organic compounds, said volatile container fractionated into a suction unit containing a volatile portion and the collection agent, the volatile portion and the discharge port of the suction portion Directly connecting each other, storing the sample of the organic material in the volatile part, volatilizing the volatile organic compound, collecting the volatile organic compound volatilized from the organic material by the adsorption part in the subsequent stage, and And A serial suction portion was measured by attaching the separately mass spectrometer, are the sum value as a structure for the analysis of organic compounds.
[0009]
In the present invention, it is very difficult to collect all organic compounds having a strong adsorptivity in a collection tube. Therefore, the container for volatilization is reduced in size, and the collection agent is combined. Then, after volatile sampling from the plastic material, the container and the collection agent are inserted into a thermal desorption gas chromatograph and measured. Thereby, it is possible to measure accurately including an organic compound having strong adsorptivity.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
An embodiment of a method for measuring organic volatiles of an organic material according to the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a diagram illustrating a measurement method according to an embodiment of the present invention. In the present embodiment, the measurement container attached to the analyzer is used as the same container including the volatile container 10 and the collection agent 12 that collect volatile organic compounds that volatilize from the organic material. FIG. 2 shows a cross-sectional view of the volatile container and the collecting agent. One of the volatile containers 10 attached to the thermal desorption-type gas chromatograph analyzer 14 is an inert gas inlet 11 having the same diameter as the outer diameter of the container, and the other is an exhaust formed in a funnel shape that is tapered from the outer diameter of the container. A quartz tube serving as the outlet 13. A cap 15 having a hole for connecting to a pipe through which an airflow flows is attached to the inlet 11. What is necessary is just to set the size of this volatile container 10 to the size which can be accommodated in the mass spectrometer demonstrated below.
[0011]
First, in order to clean the volatile container before the measurement, the collection agent 12 is filled on the discharge port 13 side inside the container. In this embodiment, the collecting agent 12 is filled with an adsorbent (trade name: Tenax). Next, it heats at 280 degreeC for about 1 to 3 hours using the heater 16 which covers an outer peripheral part of a container, distribute | circulating an inert gas from the inlet 11. FIG. Thereby, the organic compound in the volatilization container 10 inner surface and collection agent which exist before collection of a volatile organic substance can be removed, and the precision of a measured value can be raised.
[0012]
FIG. 3 shows volatile organic matter sampling from the sample. A plastic agent sample 18 is inserted between the collection agent 12 through the inlet 11 of the cleaned volatile container 10. Next, the measurement temperature is set to room temperature or a temperature at which volatilization is desired to be evaluated, and clean air or inert gas is allowed to flow from the inlet 11 toward the outlet 13 while the organic compound volatilized from the sample 18 is passed to the collector 12 Collect and sample volatile organic compounds. At this time, in the case of an organic compound having a strong adsorption force, it is adsorbed on the inner wall of the volatile container 10 before being collected by the post-volatilization collection agent 12. After sampling the volatile organic compound, the sample 18 is taken out from the volatile container 10.
[0013]
FIG. 4 shows a location where the volatile organic compound in the volatile container and the collecting agent is collected. Volatile organic compounds are collected on the inner wall of the volatile container 10 and the collection agent 12.
Next, the collected volatile organic substances are measured. As shown in FIG. 1, the entire volatile container 10 is attached to the thermal desorption apparatus of the thermal desorption gas chromatograph analyzer 14. The entire volatile vessel 10 is heated by a thermal desorption apparatus (TDT) 20 to perform thermal desorption, and the collected organic compound is injected into a gas chromatograph part (GC) 22 and a mass analysis part (MS) 24 to Measure type and quantity.
[0014]
Although the above description demonstrated the structure which filled the collection agent 12 in the volatile container 10, FIG. 5 shows the structure which isolate | separated the volatile container into the volatile part and the adsorption | suction part. The idea is basically the same as the collection method described above, but comprises a volatilization unit 25 containing the sample 18 and an adsorption unit 28 filled with the collection agent 12 as a volatilization container 25 that can be directly attached to the analyzer. Two quartz tubes are used. The discharge ports of these two tubes are connected symmetrically by a fluorine resin (registered trademark Teflon) tube 30 so that the airflow flows only in the quartz tube. After sampling as described above, the measuring method is to measure the volatile unit 26 and the adsorbing unit 28 separately by the analyzer, and the total value is used as the analysis value of the organic volatile matter. For this reason, while the collection area of the volatile organic compound from the sample 18 spreads, it can measure with a sufficient precision by increasing the quantity of the collection agent 12. FIG.
[0015]
In the embodiment according to the present invention, the volatilization containers 10 and 25 have been described using a quartz tube. However, the quartz tube is made of a silicon material, and the collector is made of silicon powder, so that it volatilizes from the plastic material. Among the organic compounds to be used, organic compounds adsorbed on the silicon surface can be measured. Moreover, the organic compound which adsorb | sucks to the material used as the object of manufactured goods can be measured by forming a volatilization container and a collection agent with the material also about metals and glass other than a silicon | silicone.
[0016]
【The invention's effect】
As described above, according to the present invention, a volatile organic compound that volatilizes from an organic material is collected in a volatile container that has been preliminarily filled with a collecting agent, and then the volatile container to which the volatile organic compound is attached is mass spectrometer. It is characterized in that the volatile organic matter is measured in a form including a volatile container and a collecting agent, and a volatile container formed by previously filling the volatile container with an organic compound collecting agent by a heat heating method. After cleaning, the volatile organic compound that volatilizes from the organic material is collected in the volatile container, and the volatile container to which the volatile organic compound is attached is attached to the mass spectrometer to attach the volatile container and the collecting agent. By adopting a configuration in which volatile organic substances are measured in a form including the above, it is possible to accurately evaluate a trace amount of an organic compound that volatilizes from an organic material, particularly adsorbs on a solid surface. This makes it possible to clarify the relationship between the selection of materials such as plastic materials constituting the clean room and the amount used, and the amount of organic compound allowed in the clean room atmosphere. Therefore, it is possible to give guidelines on the influence of organic compounds contained during the development of clean room components.
[Brief description of the drawings]
FIG. 1 is a diagram showing a measurement method according to the present embodiment.
FIG. 2 is a cross-sectional view of a volatile container and a collecting agent.
FIG. 3 is a diagram showing volatile organic substance sampling from a sample.
FIG. 4 is a diagram showing a location where a volatile organic compound is collected.
FIG. 5 is a diagram showing a separation type of a volatile part and an adsorption part.
FIG. 6 is a schematic diagram of a conventional method.
[Explanation of symbols]
1 ......... Test specimen, 2 ...... Chamber, 3 ......... Invinger, 4 ......... Collector, 10 ......... Volatile container, 11 ......... Inlet, 12 ......... Collector, 13 ......... Exhaust port, 14 ......... thermal desorption gas chromatograph analyzer, 15 ......... cap, 16 ......... heater, 18 ......... sample, 20 ...... thermal desorption device (TDT), 22 Gas chromatograph (GC) 24 Mass spectrometer (MS) 25 Volatile container 26 Volatile part 28 Adsorber 30 Fluorine resin tube

Claims (2)

A sample of an organic material was inserted between the inlet of a volatile container pre-filled with a collection agent and the collection agent, and after the volatile organic compound volatilized from the organic material was collected, the volatile organic compound adhered. wherein by mounting the volatile container each mass spectrometer, a the volatile container and organic volatiles measuring method of the organic material of the measurement of the volatile organic compounds in the form including the collection agent, the volatile container Separating into a volatilizing part and an adsorbing part containing a collecting agent, directly connecting the volatilizing part and an outlet of the adsorbing part, and containing the sample of the organic material in the volatilizing part, the volatile organic compound The volatile organic compound that volatilizes from the organic material is collected by the adsorption unit at the subsequent stage, and the volatile unit and the adsorption unit are separately mounted on a mass spectrometer and measured, and the total value is organic Analytical value of the compound The organic volatiles measuring method of the organic material, characterized by. After a volatile container previously filled with an organic compound collector is cleaned by a heat heating method, a sample of organic material is inserted between the inlet of the volatile container and the collector, and the volatile By collecting a volatile organic compound that volatilizes from an organic material in a container and attaching the volatile container to which the volatile organic compound is attached together with a mass spectrometer, the volatile container and the collecting agent are included in the form. an organic volatiles measuring method of the organic material of the measurement of volatile organic compounds, said volatile container fractionated into a suction unit containing a volatile portion and the collection agent, the volatile portion and the suction portion discharge port with each other The volatile organic compound is volatilized by accommodating the sample of the organic material in the volatile part, and the volatile organic compound volatilized from the organic material is collected by the adsorption part in the subsequent stage, and the volatile part And said A wear portion was measured by mounting the mass spectrometer separately, organic volatiles measuring method of the organic material, which comprises the sum and analysis of organic compounds.

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