JP2011021928A - Method for selecting halogen-based flame retardant-containing resin for mold forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for selecting a halogen-based flame retardant-containing resin for mold forming by achieving a composition analysis even of a minute amount of a component contained in an inorganic component derived from a flame retardant or the like by rapid and highly accurate quantification analysis. <P>SOLUTION: The method for selecting a halogen-based flame retardant-containing resin for mold forming includes the steps of: micronizing a resin containing a halogen-based flame retardant by freeze-pulverization; and, regarding the micronized resin, performing qualitative analysis of an inorganic component after press-molding and measuring the concentration of an ionic component in an extracted liquid obtained by mixing with pure water, and selects a resin whose inorganic component concentration and/or ionic component concentration is/are low based on the results of the qualitative analysis of the inorganic component and the measurement of the concentration of the ionic component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for selecting a halogen-containing flame retardant-containing resin for molding with a mold, for example, a low-pressure circuit breaker mold.

  There are many materials that can be used for flame retardants, but in many cases bromine is most effective. Bromine is more effective than most alternatives in the combustion process, and requires a small amount of flame retardant to be added to the material, providing a flame retardant effect. As a result, the color, strength and durability, which are the inherent characteristics of the material, can be maintained as they are.

  On the other hand, even in incineration, which is an environmental problem, it is scientifically clear that dioxins / furans are not generated at high temperatures (above 850 ° C.). Generates extremely harmful dioxins (Non-patent Document 1). Antimony trioxide is usually used in combination with organic brominated flame retardants, but this reacts to generate antimony bromide to help block oxygen, which is also harmful.

Therefore, it is important to know the amount of bromine (Br ⁻ ) that decomposes a part of the organic bromine compound, the halogen-based component, and other inorganic components for obtaining the type and amount of the additive component.

  Patent Document 1 shows a method for qualitatively and quantitatively dissolving a brominated flame retardant with a solvent. Non-Patent Document 2 shows a method of performing a pretreatment for extracting a brominated flame retardant into an organic solvent and then analyzing it by an MS method (gas chromatography mass spectrometer).

  Due to environmental problems since the 1990s, the movement to eliminate brominated flame retardants has spread in Europe. Examples include environmental labels in Germany and Northern Europe, and the European Union (EU) RoHS Directive (Directive to Restrict Use of Specific Hazardous Substances in Electrical and Electronic Equipment) established in January 2003. The directive stipulated that PBB (polybrominated biphenyl) and PBDE (polybrominated diphenyl ether) among brominated flame retardants should not be used in electrical and electronic products. Here, the measurement method of the specific harmful substance of the brominated flame retardant is based on the GC-MS method.

In general, inorganic components can be analyzed simultaneously by fluorescent X-rays described in Non-Patent Document 3, for example. As another analysis method, Non-Patent Document 4 also describes an ion chromatographic method, which is a quantitative analysis method of a sample solution obtained by extracting ions such as bromine ions (Br ⁻ ).

JP 2006-322817 A

Japan Flame Retardant Association Halogen Division Related Materials Survey report on management system for certification of heavy chemical substances in products, March 2004, Fuji Research Institute, Ltd. "Analytical Chemistry Handbook" revised 5th edition, pages 18-20, Japan Analytical Chemical Society edited by Maruzen Co., Ltd., December 15, 2001, JIS K 0101 (Industrial water test method)

  In the production of a halogen-containing flame retardant-containing resin, for example, in the production of a low-voltage circuit breaker (wiring circuit breaker / leakage circuit breaker), for example, there is a problem of metal corrosion of a mold due to outgas generated in an injection molding process of a resin material. This is considered to originate from the halogen flame retardant. In general, the solubility of the flame retardant in water is small, resulting in an outgas generated in the injection molding process, and the amount of dissolved ions is thought to lead to a relationship with metal corrosion. When the mold is corroded, a bad odor is emitted and the working environment is deteriorated.

  The type and amount of the flame retardant that causes corrosion may be a trade secret of the manufacturer and may not be disclosed. Further, even if the type and blending amount of the flame retardant in the resin product are disclosed, it may not always correlate with the amount of the flame retardant-derived mold corrosive component eluted in the injection molding process or the like. Furthermore, the mold corrosive component due to outgas generated in the injection molding process or the like varies depending on the resin composition, for example, a combination of a flame retardant and a polymer. Therefore, it is necessary to analyze the amount of mold corrosive components eluted in the injection molding process or the like before the resin product is used for mold molding.

  Moreover, even if the same resin product is used, the influence of the lot is large, and the amount of the mold corrosive component eluted in the injection molding process or the like may vary depending on the lot. Therefore, even when the same resin product is continuously used, it is necessary to continuously check the elution amount of the flame retardant.

  Thus, it is important to analyze the performance of the resin used for mold molding and to analyze the composition of the types and ions of inorganic elements for material management. In particular, it is necessary to establish a method for analyzing mold corrosion components due to outgas generated in the injection molding process of resin materials. A method for quantitative analysis is required.

  However, Patent Document 1 only shows a method for qualitatively and quantitatively dissolving a brominated flame retardant with an organic solvent, and a method for analyzing and examining the amount of water-soluble ions related to metal corrosion on the mold in the resin. There was no literature such as. In particular, paying attention to the analysis of the amount of ions related to mold corrosion, there is a need for a method for establishing an analytical method derived from a flame retardant in a resin and managing the material.

  Non-Patent Document 2 describes a management method of an organic bromine-based flame retardant containing bromine by pretreatment for extraction into an organic solvent as a brominated flame retardant, and then using a GC-MS method (gas chromatography mass spectrometer). Although it shows, it is different from the previous ion amount analysis in which the composition analysis of the kind of inorganic element and the ion amount for the performance investigation and material management of the flame retardant is performed.

The X-ray fluorescence analysis method described in Non-Patent Document 3 is a pretreatment of a solid sample containing each component of an inorganic component composed of an inorganic component derived from a flame retardant or an additive component in a sample used for a resin for a low pressure circuit breaker. And the application of analytical methods is not exhaustive. In general, the ionic component described in Non-Patent Document 4 is also a sample of a solution sample for the ion chromatographic method, and the method is only introduced. The flame retardant and additive component of the resin to be analyzed No mention is made of pretreatment and inorganic analysis application to the derived inorganic components. The same applies to the example of “Analysis method of Br ⁻ ” defined in Non-Patent Document 4 regarding bromine and chlorine as halogen elements of flame retardants.

  By the way, the inorganic element analysis derived from the flame retardant and additive component in the resin includes a halogen, a metal element, and a filler component. Therefore, a sample preparation method (pretreatment) for each resin analysis method is required. In addition to organic bromine compounds, it is important to clarify the total inorganic content of inorganic components that require the type and amount of flame retardants, and in particular to know the amount of water-soluble ions related to metal corrosion of molds. .

  The present invention has been made to solve the above-described problems, and its purpose is to quickly and accurately analyze the composition of trace amounts of inorganic components derived from flame retardants and the like. It is an object of the present invention to provide a method for selecting a halogen-containing flame retardant-containing resin for molding a mold by quantitative analysis.

  In order to achieve the above-mentioned object, the inventor considers that it is important to know the amount of water-soluble ions related to metal corrosion of a mold prior to component analysis of a resin sample. It was found that the whole was grasped, and then the amount of water-soluble ions related to corrosion was analyzed. Therefore, by clarifying the conditions of pretreatment methods and equipment, it is possible to establish an analysis method for inorganic and ionic components that is simple but highly accurate, and that determines the types and amounts of halogen-based components and other additive components. The idea is to solve the above problems.

  That is, the present invention is a method for selecting a halogen-based flame retardant-containing resin for molding a mold, the step of freezing and pulverizing a resin containing a halogen-based flame retardant, and the atomized resin. In contrast, qualitative analysis of the inorganic component by pressure molding and a step of measuring the concentration of the ionic component of the extract obtained by mixing with pure water, the qualitative analysis of the inorganic component and the ion Based on the measurement result of the component concentration, a resin having a low concentration of the inorganic component and / or the ionic component is selected.

According to the method for analyzing an additive component in a resin performed in the present invention, qualitative analysis and quantification of Br, Cl, F, and Sb such as a halogen element derived from a flame retardant in the resin in advance based on the measurement result of the inorganic component. Analyze, confirm existence and manage materials. For example, the degree of ions related to metal corrosion of the mold can be analyzed and inspected from the halogen ions described later and the detected 14 ion species.
In the present invention, it is important to know the amount of water-soluble ions related to metal corrosion of the mold of a resin sample, and the whole is understood by analysis of inorganic elements in the resin, and then the amount of water-soluble ions related to corrosion By analyzing the above, it is possible to provide a method for selecting a halogen-based flame retardant-containing resin for molding a mold.

FIG. 1 is a flowchart showing an outline of a processing procedure of a method for selecting a halogen-containing flame retardant-containing resin for molding a mold according to the present invention. FIG. 2 is a diagram for explaining the procedure of a method for measuring an inorganic component of a resin by fluorescent X-ray analysis. FIG. 3 is a schematic diagram illustrating the configuration of a general fluorescent X-ray analyzer. FIG. 4 is a diagram for explaining the procedure of the method for measuring the ionic component concentration of the resin extract. FIG. 5 is a schematic diagram illustrating a flow path of a general ion chromatograph. FIG. 6 is a graph showing the relationship between the bromine ion recovery rate and the extraction time when extracted using ultrasonic waves. FIG. 7 is a graph showing an example of a chromatogram of an anion standard solution. FIG. 8 is an example of a calibration curve graph showing the relationship between the peak area and concentration of bromine ions in ion chromatography.

  The method for selecting a halogen-based flame retardant-containing resin for molding a mold according to the present invention will be described in more detail below. The present invention is not limited to the following embodiments.

  The material to be injection molded is generally granular plastic (thermoplastic, thermosetting) (crystalline, amorphous) (biodegradable plastic), etc., but the resin is not only used alone but also glass fiber, It is often reinforced by mixing carbon fibers. The resin in this case is polybutyl phthalate (PBT: with glass fiber), polyetherimide (PEI: with glass fiber), 6T nylon (with glass fiber), etc., and the state of the sample includes pellets and molded products . In addition, colorants can be mixed to color a wide range, and composite parts can be made by inserting multi-material molding or metal parts. In the injection molding process, the material is melted and flowed (in a mold) with a machine called an injection molding machine, and then molded into a shape to make a molded product.

  The mold is kept at a relatively low temperature so as to promote the flow of hot water in which the resin is dissolved and to cool and solidify. The temperature is controlled by a temperature-controlled band heater or the like. A mold is a mold with an inverted shape of the desired shape. Since a large pressure is required when a product material is poured into a mold and a mechanism for extruding a molded product from a mold, a main body that can withstand the pressure is required. Further, each component of the mold is mainly made of a metal material because it requires high strength. The type of mold depends on the material of the product: (1) Press mold, (2) Plastic mold, (3) Die casting mold, (4) Rubber mold, (5) Ceramic mold, (6) Glass mold It is classified into a die, (7) a casting die, and (8) a forging die. Among these, the corrosion caused by the halogen-based flame retardant is a problem in press dies, die casting dies, and casting / forging dies. The mold is preferably a low pressure circuit breaker mold.

In general, after the breaker is manufactured and manufactured, the resin is thermally decomposed when ignited to generate a combustible gas (hydrocarbon, CO, etc.). Since this decomposition product undergoes a radical reaction with oxygen and burns, a cycle in which thermal decomposition further proceeds due to heat generated at that time.
RH → R ・ + H ・
R ・ + O ₂ → ROO ・
ROO ・ + RH ・ → ROOH + R ・
ROOH → RO ・ + OH ・
Therefore, conventionally, halogen flame retardants have been mainly used as a flame retardant from the viewpoint of excellent flame retardant effect and low cost with bromine and chlorine. A typical one is an organic bromine compound.

  The present invention includes a resin pretreatment method for analyzing components added to the resin. This pretreatment method is characterized by first obtaining a solidified sample by pressure molding a pretreatment method for analyzing an inorganic component of a resin. Even if the sample is in the form of a pellet or a molded product, it can be atomized by freeze pulverization to about 100 μm or less. It is desirable to homogenize and prepare the powder by a hydraulic method. Next, in the pretreatment method of the extraction method in the resin, after the resin is freeze-pulverized and atomized, the extraction is performed in order to increase the extraction efficiency of the aqueous solution obtained by applying ultrasonic waves.

  FIG. 1 is a diagram illustrating an example of a procedure of a method for selecting a halogen-based flame retardant-containing resin for molding a mold according to the present invention. FIG. 1 shows the application of the pulverization method 2 and the pretreatment method in the analysis of the additive component in the resin sample of Start 1, and in this figure, the sample preparation method for each analysis object, that is, extraction 7 and filtration recovery 8 4 and pressure forming 5, and the fluorescent X-ray analysis method 6 or the analysis method of the ion chromatograph method 9 and the data analysis 10 are shown. This sample contains an inorganic component of the additive component in the resin and an extracted ionic component. After applying the pretreatment method described later to such a sample, the component amount of the additive component in the resin is preferably analyzed by the fluorescent X-ray analysis method 6 and the ion chromatography method 9. Reference numeral 11 indicates an end.

First, FIG. 1 shows that the powder is weighed 3 with a balance after freeze pulverization 2 in the sample preparation method. Thereafter, the sample preparation method, analysis method, and data processing unit for each analysis target are performed. Although details will be described later, the freeze pulverization 2 will be described first.
In the freeze pulverization method, an impactor (iron core) and a sample are put together in a pulverization container and immersed in liquid nitrogen. The impactor is reciprocated by using an electromagnet after the sample is frozen, and the sample is pulverized when it collides with the end plug (iron cover). At this time, the particle size is preferably about 100 μm or less. The preferable average particle diameter of the pulverized powder is 20 to 200 μm as measured by a sieving method. For screening, a test sieve according to JISZ8801 is used. There are pellets and molded products in the state of the sample of Start 1, and it is necessary to miniaturize for subsequent pressure molding and efficiency of ion analysis extraction. This is then used to enter the weighing 3 step. In the step of weighing 3, the freeze-pulverized powder is weighed with a balance to an amount necessary for analysis, for example, 0.1 mg.

[Resin powder pressure molding method and inorganic component measurement method]
FIG. 2 illustrates an example of a procedure of a method for measuring an inorganic component of a resin sample by a fluorescent X-ray analysis method. The pretreatment method of the inorganic component performed prior to the component analysis of the resin sample is performed by applying a direct powder pressure molding method (hereinafter simply referred to as pressure molding) of the resin sample in which the sample is directly pressed and molded. To solidify. The powder pressure molding method and the inorganic component measurement method for resin samples will be described below.

  In the pre-processing method for pressure molding, first, from the resin to be analyzed at the start (step S101), a powder sample of the resin to be analyzed is prepared (step S102). S103). Next, this is mixed with a binder described later (step S104) and pressure-molded (steps S105A and S105B). And the component of the shape | molded molded object is analyzed with the analyzer of the fluorescent X ray method mentioned later (step S106). Thereafter, data analysis is performed (step S110).

  Specifically, the aluminum ring pressure forming method is applied to the pressure forming in step S105. In this aluminum ring pressure molding method, for example, a powdered sample is filled on the inner diameter side of an aluminum ring hollowed out in a donut shape having an outer diameter Φ45, an inner diameter 43Φ, and a height of 5 mm. In a state where the sample is filled on the inner diameter side, the two organic thin films (mylar film, step S105) are sandwiched from both sides. Then, pressure is applied from the base of the hydraulic device so as to sandwich these organic thin films. For this reason, since the resin sample is sandwiched between organic thin films, impurities do not adhere to the analysis surface.

  The pressure molding of the present invention solidifies the sample in this way. The solidified resin sample is determined by a fluorescent X-ray analyzer using, for example, Φ25 as an analysis surface from its approximate center.

  FIG. 3 shows an example of a fluorescent X-ray analyzer (optical unit). A resin powder pressure-molded body sample is disposed at the sample position 17. Here, the analysis sample is irradiated with primary X-rays 13 generated from the X-ray tube 12. The fluorescent X-ray 14 is unique to the constituent element of the sample generated from the analysis sample, can be qualitatively analyzed from the difference in wavelength, and can be quantitatively analyzed by the relative intensity compared to the standard sample of that intensity. The fluorescent X-ray 14 is dispersed by the spectral crystal 15, and the characteristic X-ray of each element is detected by the detector 16. Thereafter, the signal is converted into an electric signal by the control unit 18 and a qualitative analysis spectrum analysis and a quantitative analysis value of the analysis sample are obtained by a measuring instrument or a data processing device. The qualitative analysis of the inorganic component (target elements 9F to 92U) and the quantitative analysis of the detection element are obtained from the relationship between the X-ray intensity and the concentration. The data processing described above can be performed by the FP method (Fundamental Parameter method).

  The analysis method of the additive component in the resin performed in the present invention is based on the results of simultaneous analysis and measurement of the inorganic component of the solidified sample using fluorescent X-ray analysis, and the atomic numbers 9 to 92 Qualitative analysis and quantitative analysis of F to U can be performed. Quantitative analysis (mass%) can be performed by the FP method using a data processing device from the relationship between the X-ray intensity of the obtained detection element and the concentration of the inorganic component. The analysis result of the inorganic component has a lower limit of quantification of 0.01% by mass, and the presence / absence is controlled at a predetermined concentration. On the other hand, the analysis result of the extracted component is effective as an investigation material for the previous component at the time of the next extracted ion analysis.

[Ion extraction method and ion concentration measurement method for resin powder samples]
FIG. 4 is a diagram for explaining the procedure of the method for measuring the ionic component concentration of the resin extract. In FIG. 4, a pretreatment method for a sample containing extracted ion components, which is performed prior to ion component analysis of a resin sample, will be described.

  In the pretreatment method of ion analysis, first, a powder sample of the resin to be analyzed is prepared from the resin at the start (step S201) (step S202), and an amount suitable for the analysis is weighed (step S203). Next, this is extracted with pure water described below (step S207) and filtered (step S208A). And what was extracted and recovered (step S208B) is analyzed for its ion components by an ion chromatograph analyzer described later (step S209). Thereafter, data analysis is performed (step S210).

  In the step of extracting the powder sample with pure water (step S207), it is preferable to perform extraction by applying ultrasonic waves. This is to increase the extraction efficiency of ionic components in the resin into pure water.

Specifically, the ion component concentration is measured with a liquid extracted into the pure water using ion chromatography. This measuring instrument has 14 components (F ⁻ , Cl ⁻ , NO ₂ ⁻ , Br ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , PO ₄ ³⁾ including anions, halogen ions, and organic acid ions depending on the apparatus conditions. ⁻ , CH ₃ COO ⁻ , HCOO ⁻ , Na ⁺ , NH ₄ ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ ). Quantitative analysis can obtain the results of simultaneous analysis of bromine ions (Br ⁻ ), chlorine ions (Cl ⁻ ) and the like as examples. In addition, quantitative analysis of other ion species is performed by applying a calibration curve to the relationship between the conductivity and concentration of the ion peak.

  The resin sample obtained by the above-mentioned pretreatment (powder ion analysis method) is subjected to quantitative analysis including halogen ions. Quantitative analysis is performed by applying a calibration curve to the relationship between the conductivity and concentration of the detected ion species. In this evaluation test, conditions such as the flow rate of the sample solution and the separation column in the ion chromatograph analyzer can be set as appropriate.

  FIG. 5 shows an example of a flow chart of a general ion chromatograph. In the ion chromatograph, a sample (extracted sample) is injected into a weak electrolyte eluent 21 from a sample injection section 23, and is passed through a separation column 24 made of an ion exchange resin, and the hydration radius is large and small in the column. The ion species are separated from each other by the interaction, and the background conductivity is lowered by passing through the suppressor 25, and the target ion species is obtained as a chromatogram with high sensitivity. The separation column 24 can be exchanged depending on the target ion component. In addition, when analyzing a cation with an ion chromatograph analyzer, the column 24 and the eluent 21 may be recombined with an ion exchange resin for cation analysis. Reference numeral 22 denotes a pump.

  The ion chromatographic method is a method in which several types of anion components can be simultaneously measured in a single measurement using a sample of several μl, and fractional quantitative analysis can be performed. The detector 26 uses a flow cell type conductivity detector, and the ion component concentration in the target analysis sample solution is obtained from the peak area and height of the ion chromatogram based on the conductivity of each ion component.

In addition, a halogen ion species can be selected from the obtained detected ion species, and the quantitative analysis results of the 14 components can be obtained. The lower limit of quantification is, for example, 0.01 μg / g, and the metal corrosion degree of the mold can be analyzed and inspected based on the result of measuring the concentration of ion components extracted in pure water.
For example, the concentration of each ion component eluted is 0.1 to 100 μg / g, and is determined by ion analysis of the resin material extract to control the corrosion of the mold. In this case, the absolute amount of the unit mass of the resin is analyzed and examined with halogen ions (F ⁻ + Cl ⁻ + Br ⁻ ) of 30 μg / g or less. This is due to the fact that there was no level of corrosion based on previous data.

The selection of the halogen-containing flame retardant-containing resin is specifically performed as follows. That is, as a result of measuring the ion component concentration, when the halogen ion (F ⁻ + Cl ⁻ + Br ⁻ ) concentration in the resin exceeds 30 μg / g, the resin material is changed. On the other hand, when the halogen ion (F ⁻ + Cl ⁻ + Br ⁻ ) concentration in the resin is 30 μg / g or less, the ion component is clarified and material management is performed. Further, although halogen ions (F ⁻ + Cl ⁻ + Br ⁻ ) are most related to corrosion, 11 components (NO ₂ ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , PO ₄ ³⁻⁾ excluding halogen among the above 14 components. , CH ₃ COO ⁻ , HCOO ⁻ , Na ⁺ , NH ₄ ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ ) are also associated with corrosion. If any one of the 11 components exceeds 30 μg / g, it is preferable to change the resin material. If the concentration of each component is 30 μg / g or less, the analysis is continued. Perform material management. The 14 components are related to the amount of hydrogen ions coexisting with anions, and the cations are related to corrosion in relation to the amount of hydroxide ions coexisting. This is thought to be due to the presence of some moisture and other moisture, which reacts with ions and corrodes the metal. In addition, although antimony, which is a flame retardant, usually becomes an oxide, it can react with bromine to become antimony bromide, which is considered to cause metal corrosion. Accordingly, if the antimony ion (III) also exceeds 30 μg / g, it is preferable to change the resin material, and if it is 30 μg / g or less, continue to analyze and manage the material. Here, the value used for selection of the resin is a value converted into the concentration per unit mass of the resin.

  Thus, the analysis method of the additive component in the resin of the present invention includes a pretreatment method in the resin for analyzing the flame retardant component added to the resin, and an inorganic component of the solidified sample using a fluorescent X-ray analysis method. And the degree of corrosion is controlled at a predetermined digitized concentration based on the elution result obtained by measuring the ion component concentration by extracting the sample into pure water using ion chromatography. This can be evaluated between samples and is useful.

  In addition, the analysis method of the additive component in the resin of the present invention is not limited to the above-described embodiment, and various modifications may be made without departing from the above of the present invention.

  The halogen-containing flame retardant-containing resin can be molded into a molded product such as a low-pressure circuit breaker by a method known to those skilled in the art. Although a shaping | molding method will not be specifically limited if a metal mold | die is used, For example, injection molding, compression molding, and extrusion molding are mentioned. For low pressure circuit breakers, injection molding is usually used.

[Analysis of inorganic components]
As a resin sample, pellets and molded articles of polybutyl phthalate (PBT: with glass fiber) were used. The inorganic component was measured by fluorescent X-ray analysis. For this fluorescent X-ray analysis, a 3272 type [X-ray tube target: Rh] wavelength dispersion type fluorescent X-ray analyzer (fluorescent X-ray apparatus) (manufactured by Rigaku Corporation) was used. Prior to the compositional analysis of the kind and ion content of inorganic elements for performance investigation and material management of resin samples, the inorganic elements of pellets and molded products were quantified by the FP method.

Below, the processing content performed in order to analyze an inorganic component is shown with a bullet.
・ Powder sample obtained by freeze grinding (average particle size: 100 μm)
・ Approximately prepare 0.5 g ・ Weigh 0.5 g of powder sample ・ Binder: Use about 0.1 g of a mixture of lithium tetraborate and stearic acid (mass ratio 1: 1) Preparation of mixing / pressure molding rack in beaker (special equipment)
・ Aluminum ring: Φ40 / 4mmt
-Organic thin film upper and lower release film: Mylar film (Φ45, 6μm thickness)
-Reinforcing binder: Uses about 2g of a mixture of lithium tetraborate and stearic acid.-Uses a manual hydraulic press (dedicated device).
・ Pressurized total pressure: 15t / pair above sample Φ45 aluminum ring filling ・ Peeling and removing organic thin film (securing the analysis surface)
・ Analytical sample: Completion, measurement, and data analysis of pressure-molded body (display: mass%)

表１より、射出成形後の成形品でも組成に大きな差はないことが分かった。添加材成分は、無機成分の測定結果から、樹脂中の難燃剤由来のハロゲン元素などＢｒ、Ｃｌ、Ｆ、Ｓｂや充填剤（Ｓｉ、Ｃａなど）の定性分析と定量分析ができ存在を確認した。定量下限は０．０１質量％であった。 Table 1 shows the measurement results of the inorganic components.

From Table 1, it was found that there was no significant difference in composition even in the molded product after injection molding. From the measurement results of the inorganic component, the presence of the additive component was confirmed by qualitative analysis and quantitative analysis of Br, Cl, F, Sb and fillers (Si, Ca, etc.) such as halogen elements derived from flame retardants in the resin. . The lower limit of quantification was 0.01% by mass.

[Analysis of bromine ion concentration]
(I) Ultrasonic Extraction FIG. 6 is a graph showing the results of a bromine ion recovery experiment “Relationship between ultrasonic extraction time and bromine ion recovery rate”, from a sample containing 2 ppm bromine ions (crushed sample, molded sample). This is a recovery experiment. In the extraction method, although the recovery time differs between the pulverized product and the molded sample, in both cases, the ultrasonic extraction time was 25 minutes or more, and the recovery was possible.

  In this extraction liquid method (pure water ultrasonic extraction method), a predetermined amount of sample is put into a conical flask with a stopper (capacity 100 ml), pure water (50 ml) is added, and an ultrasonic cleaning device (UO300FB: voltage 100V, The aqueous solution was extracted with a current of 6 A, a rated output of 300 W, an oscillation frequency of 26 kHz, manufactured by Shinmei Kogyo Co., Ltd. The effect of this pure water extraction method was analyzed by the amount of bromine ions to determine the recovery rate.

(II) Analysis by Ion Chromatograph FIG. 7 is an example of a chromatogram (anion), and FIG. 8 is a graph showing the target extracted sample solution based on the peak area and height of the ion chromatogram based on the conductivity of the ion component. It is an example of the calibration curve of bromine ion which calculated | required the ion component density | concentration of. Next, an example of anion analysis conditions is shown, and the analysis result of bromine ions is shown.

An example of anion analysis conditions in ion chromatography is shown below.
(1) Method: Ion chromatograph analyzer for anion (DX-320, manufactured by DIONEX)
(2) Separation column: Ion Pac AS17 / Ion Pac AG17 (manufactured by DIONEX)
(3) Eluent: EGC-KOH (manufactured by DIONEX) (potassium hydroxide 10 mM start step gradient)
(4) Removal system: Auto suppressor (ASRS)
(5) Sample liquid volume 10 μL loop method (6) Quantitative method: calibration curve method of ion chromatogram peak area and ion component concentration

FIG. 8 shows a calibration curve of the peak area intensity of bromine ions and the ion concentration (ppm). The empirical formula in the calibration curve is a formula obtained by regression analysis of the obtained straight line, and the bromine ion concentration (ppm) = 2.816x + 0.021. Note that x in this equation represents area intensity, and the correlation coefficient is R ² = 0.9996.
Next, examples of 14 ion components will be described. In the analysis of the actual sample described below, data processing was performed using a calibration curve.

[Analysis of ion component concentration]
As a resin sample, pellets and molded articles of polybutyl phthalate (PBT: with glass fiber) were used. This is a quantitative analysis of the composition of the extracted ions for performance investigation and material management. Below, the processing content performed for the measurement of an ion component is shown in a bullet.
・ Powder sample obtained by freeze grinding (average particle size: 100 μm)
・ Prepare approximately 2.0 g.
・ Weighing about 2.0 g of powder sample ・ Preparation for extraction: Inject the above-mentioned weighed product into a predetermined flask equipped with a stopper together with 1000 ml of ultrapure water extract.
・ Preparation of filtration and recovery of 1000 ml of extraction liquid ・ Ion concentration measurement in extraction liquid recovery liquid ・ Ion concentration is also measured in standard liquid ・ Ion amount per unit mass is calculated from the measured ion concentration in liquid. (Display: μg / g)
・ Data analysis

Table 2 shows the results of quantitative analysis of 14 components containing halogen ions.

The previous resin (PBT) contained 10% level of bromine in pellets and molded articles (Table 1). According to Table 2, the Br ⁻ content was 1 μg / g or less in the halogen ion analysis. From this, it was found that the resin sample generally contains a large amount of brominated flame retardant, and the amount of Br ⁻ eluted as ions is relatively small.

  According to the present invention, a halogen-containing flame retardant for molding is contained by quantitative analysis of the composition analysis quickly and with high accuracy even for a trace amount component contained in an inorganic component derived from a flame retardant and the like. A method of selecting a resin can be provided.

1 Start 2 Freeze pulverization 3 Weighing 4 Mixing 5 Pressure molding 6 Analysis of solid of analysis sample (fluorescence X-ray analysis method)
7 Extraction 8 Filtration and recovery 9 Ion analysis of analysis sample (ion chromatography)
10 data analysis 11 end 12 X-ray tube 13 primary X-ray 14 fluorescent X-ray 15 spectroscopic crystal 16 detector 17 sample position 18 control unit 21 eluent 22 pump 23 sample injection unit (extraction sample)
24 Separation column (column exchangeable)
25 Suppressor 26 Conductivity detector 101 Start 102 Frozen ground resin powder sample 103 Weighing 104 Mixing 105A Pressure molding stand installation 105B Pressure molding 106 Analysis of pressure molded body sample (X-ray fluorescence analysis)
110 Data analysis 201 Start 202 Powder sample of frozen pulverized resin 203 Weighing 207 Extraction 208A Filtration 208B Recovery 209 Ion analysis of extracted sample (ion chromatography fluff method)
210 Data analysis

Claims (8)

Freezing and pulverizing a resin containing a halogen-based flame retardant,
A step of subjecting the atomized resin to pressure analysis and qualitative analysis of inorganic components, and measurement of the concentration of ionic components in an extract obtained by mixing with pure water.
Based on the qualitative analysis of the inorganic component and the measurement result of the concentration of the ionic component, a resin containing a halogen-based flame retardant for molding is selected that selects a resin having a low concentration of the inorganic component and / or the ionic component. Method. The qualitative analysis of the inorganic component is a qualitative analysis of fluorine, chlorine, and bromine, and the measurement of the concentration of the ionic component is measurement of the concentration of fluorine ion, chlorine ion, and bromine ion,
2. The halogen-based difficulty for molding a mold according to claim 1, wherein the resin having a low concentration of the ionic component is a resin having a total concentration of the ionic component of 30 μg / g or less in terms of a unit mass of the resin. A method of selecting a resin containing a flame retardant. The qualitative analysis of the inorganic component further includes qualitative analysis of sulfur, phosphorus, sodium, potassium, magnesium, calcium, and antimony, and the measurement of the concentration of the ionic component further includes nitrite ion, nitrate ion, sulfate ion Measurement of the concentration of 11 components of phosphate ion, acetate ion, formate ion, sodium ion, ammonium ion, potassium ion, magnesium ion, and calcium ion,
The halogen-based molding die according to claim 2, wherein the resin having a low concentration of the ionic component is a resin in which the concentration of each of the 11 components is 30 µg / g or less in terms of unit mass of the resin. A method of selecting a flame retardant-containing resin. The qualitative analysis of the inorganic component further includes a qualitative analysis of antimony, and the measurement of the concentration of the ionic component further includes measurement of the concentration of antimony ions,
4. The halogen-based difficulty for molding a mold according to claim 2, wherein the resin having a low concentration of the ionic component is a resin having an antimony ion concentration of 30 μg / g or less in terms of unit mass of the resin. A method of selecting a resin containing a flame retardant.   The method for selecting a halogen-based flame retardant-containing resin for molding a mold according to any one of claims 1 to 4, wherein the ion concentration is measured using ion chromatography.   The method for selecting a halogen-based flame retardant-containing resin for molding a mold according to any one of claims 1 to 5, wherein the qualitative analysis of the inorganic component uses a fluorescent X-ray analysis method.   The method for selecting a halogen-containing flame retardant-containing resin for molding a mold according to any one of claims 1 to 6, wherein the resin containing the halogen-based flame retardant to be freeze-ground is a molded product or a pellet.   A method for producing a low-pressure circuit breaker comprising a step of molding a halogen-containing flame retardant-containing resin selected by the method according to any one of claims 1 to 7 with a mold.

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