Tin phosphide and method for producing tin phosphide

Abstract

The present invention provides tin phosphide which has reduced ignitability.　Provided is tin phosphide in which ignition does not occur when 3 mL of the tin phosphide is placed on a heat insulation plate and cerium-iron sparks are applied to the tin phosphide 1-50 times from a position 5 mm away from the tin phosphide, wherein the ratio Sn / P (by weight) of tin to phosphorus is 8.4-13.3, and a simple substance of phosphorus and / or phosphorus-rich tin phosphide is not substantially contained.

Description

Tin Phosphide and Method for Producing Tin Phosphide

[0001] The present invention relates to tin phosphide and a method for producing tin phosphide.

[0002] Tin phosphide, which is a compound of tin (Sn) and phosphorus (P), has attracted attention for its applications in recent years. Tin phosphide exists in various forms such as tin tetraphosphide (Sn ４ P ３ ), tin triphosphide (Sn ３ P ２ ), tin tritophosphide (Sn ３ P ４ ), tin monophosphide (SnP ３ ), etc. Among these, tin tetraphosphide (Sn ４ P ３ ) is an industrially promising material, and various application developments have been explored. Regarding the "tin phosphide and method for producing tin phosphide" of the present invention, tin tetraphosphide (Sn ４ P ３ ) is targeted, and hereinafter, tin tetraphosphide (Sn ４ P ３ ) will be referred to as "tin phosphide".

[0003] Such tin phosphide has been experimentally produced by various methods. For example, Patent Document 1 describes a method for producing tin phosphide (vapor deposition method) in which pulverized powder of phosphorus and tin are mixed, compression molded into a film shape, and a pulsed laser is applied thereto to deposit tin phosphide.

[0004] In addition, Patent Document 2 describes a method for producing tin phosphide (gas phase method) in which phosphorus and tin are added to a reactor, heated for a predetermined time under a vacuum atmosphere or an inert gas atmosphere, then cooled, and the cooled reaction product is washed and dried to obtain tin phosphide.

[0005] Specification of Chinese Patent Application Publication No. 101289176 Specification of Chinese Patent Application Publication No. 112978693

[0006] By the way, since tin phosphide has the property of being prone to ignition, there has been a demand for tin phosphide with a less flammable and safer property.

[0007] Tin phosphide is generally manufactured using metallic tin and red phosphorus as raw materials. Although red phosphorus, as a pure form of phosphorus, does not have the same high reactivity as yellow phosphorus, it is still designated as a Class II hazardous material under the Fire Service Act in Japan. Because it is easily ignited by flame, extreme caution is required when handling it. In the case of tin phosphide, ignition can sometimes occur due to residual red phosphorus from the raw materials. Although the risk of ignition of tin phosphide was potentially recognized, industrial production was rarely carried out, and as a result, no countermeasures have been taken for conventional tin phosphide, including those described in the aforementioned Patent Documents 1 and 2.

[0008] This invention has been made in view of the above-mentioned problems, and aims to provide tin phosphide with reduced ignition properties. Furthermore, it aims to provide a method for producing tin phosphide that enables the industrial production of such tin phosphide with reduced ignition properties.

[0009] The characteristic configuration of tin phosphide according to the present invention for solving the above problems is that, when 3 mL of the tin phosphide is placed on an insulating plate and a cerium-iron spark is applied to the tin phosphide 1 to 50 times from a position 5 mm away from the tin phosphide, no ignition is observed.

[0010] The method employed in this invention, "placing 3 mL of tin phosphide on an insulating plate and applying a cerium-iron spark to the tin phosphide from a distance of 5 mm to determine its ignition properties," is a test method that conforms to the cerium-iron spark test, which serves as an indicator of ignition properties as defined by the German Federal Institute for Materials Research and Testing (BAM). With this configuration of tin phosphide, even when a cerium-iron spark is applied to the tin phosphide 1 to 50 times using a method conforming to the ignition properties test defined by the German Federal Institute for Materials Research and Testing (BAM), no ignition can be confirmed, thereby providing industrially useful tin phosphide with reduced ignition properties.

[0011] In the tin phosphide according to the present invention, the ratio of tin to phosphorus, Sn / P (by weight), is preferably 8.4 to 13.3.

[0012] According to the tin phosphide of this structure, by setting Sn / P (weight) to 8.4 to 13.3, while ensuring the properties of tin phosphide, phosphorus that is likely to ignite is not excessively contained in the tin phosphide. Therefore, it is possible to obtain high-quality tin phosphide with reduced ignition properties.

[0013] In the tin phosphide according to the present invention, it is preferable that substantially no elemental phosphorus and / or phosphorus-rich tin phosphide is contained.

[0014] According to the tin phosphide of this structure, since substantially no elemental phosphorus that is easy to burn and / or phosphorus-rich tin phosphide with a high phosphorus ratio during the reaction is contained, it is possible to obtain tin phosphide with further reduced ignition properties.

[0015] In the tin phosphide according to the present invention, in the volume integral distribution of the particles, the ratio of the 50% particle size (D ５０ ) is preferably 6 to 9%.

[0016] According to the tin phosphide of this structure, by setting the ratio of the 50% particle size (D ５０ ) to 6 to 9%, even for a powder property that is generally easy to ignite, the ignition property of the tin phosphide can be further reduced.

[0017] In the tin phosphide according to the present invention, in the volume integral distribution of the particles, (a) the 10% particle size (D １０ ) is 1.8 to 11.4 μm, and (b) the 90% particle size (D ９０ ) is preferably 21.7 to 386.5 μm.

[0018] According to the tin phosphide of this structure, by making the tin phosphide have the particle size distributions of (a) and (b) above, even for a powder property that is generally easy to ignite, the ignition property of the tin phosphide can be further reduced. Also, since the particle size distribution of the tin phosphide becomes appropriate, it becomes easier to handle as a powder.

[0019] Furthermore, the characteristic configuration of the present invention for the method of producing tin phosphide to solve the above problems preferably includes: an input step of adding tin, red phosphorus, and an amine-based solvent to a reaction vessel; a reaction step of sealing the reaction vessel and heating it while stirring; a cooling step of cooling the reaction vessel; a filtration step of removing the contents from the reaction vessel and filtering out the tin phosphide; a washing step of washing the filtered tin phosphide; and a drying step of drying the washed tin phosphide.

[0020] According to the tin phosphide manufacturing method of this configuration, tin phosphide with reduced ignition properties can be industrially produced by a solvothermal process that encompasses each of the above-mentioned steps.

[0021] In the method for producing tin phosphide according to the present invention, it is preferable that the ratio of tin to red phosphorus, Sn / P (by weight), is set to 5.0 or more in the input step.

[0022] According to the present method for producing tin phosphide, by setting the Sn / P (weight) ratio of tin to red phosphorus to 5.0 or higher in the input step, the performance of tin phosphide is ensured while preventing an excess of easily ignitable phosphorus from being included in the tin phosphide. As a result, high-quality tin phosphide with reduced ignition properties can be produced.

[0023] In the method for producing tin phosphide according to the present invention, the amine-based solvent is preferably ethylenediamine and / or diethylenetriamine.

[0024] According to this method for producing tin phosphide, since red phosphorus is readily soluble in ethylenediamine, using ethylenediamine as the amine solvent in the solvothermal process allows the red phosphorus to efficiently contact tin while dissolved in ethylenediamine, thereby increasing the reactivity between tin and red phosphorus. A similar effect can be expected when red phosphorus is dissolved in diethylenetriamine. Therefore, less unreacted red phosphorus remains in the produced tin phosphide, making it possible to produce high-quality tin phosphide with reduced ignition properties. Furthermore, the reaction process between tin and red phosphorus can be carried out more safely.

[0025] In the method for producing tin phosphide according to the present invention, it is preferable that in the washing step, the tin phosphide is washed with water and then washed with ethanol.

[0026] According to the present method for producing tin phosphide, the tin phosphide is first washed with water to remove unreacted red phosphorus and / or a small amount of phosphorus-rich tin phosphide with a high phosphorus ratio remaining during the reaction, and also to remove any amine-based solvents adhering to the tin phosphide. The removal of the amine-based solvent can be confirmed by the pH of the tin phosphide surface becoming near neutral. Next, the tin phosphide is washed with ethanol to replace and remove any remaining moisture, and by drying it, high-quality tin phosphide with reduced flammability can be produced.

[0027] Figure 1 is a schematic diagram showing an overview of the cerium-iron spark ignition test. Figure 2 is a flowchart showing a method for producing tin phosphide according to an embodiment of the present invention, where (a) is a flowchart showing the overall method for producing tin phosphide according to an embodiment of the present invention, (b) is a flowchart showing the details of the reaction process, and (c) is a flowchart showing the details of the washing process.

[0028] According to the present invention, tin phosphide (Tetraten triphosphide (Sn ４ P ３ The present invention will describe the methods for producing )), and tin phosphide. However, the present invention is not limited to the configurations described in the embodiments and examples below.

[0029] <BAM Ignition Test> The tin phosphide according to the present invention is tin phosphide having reduced ignition properties. Here, the evaluation of the ignition properties of a substance is often carried out by the test method established by the German Federal Institute for Materials Research and Testing (BAM) (hereinafter referred to as the "BAM ignition test"), and the BAM ignition test has become the de facto industry standard. Therefore, we will first explain the outline of the BAM ignition test.

[0030] The BAM ignition test includes the small gas flame test, the red-hot iron rod test, the fuse test, and the cerium-iron spark ignition test. Of these, the cerium-iron spark ignition test is a test method that determines whether a substance is easily ignited by an external spark, and is suitable for confirming the ignition properties of compounds made from a substance that is inherently easily ignited (red phosphorus in this invention) as a raw material.

[0031] Figure 1 is a schematic diagram showing an overview of the cerium-iron spark ignition test. As shown in Figure 1, the cerium-iron spark ignition test involves placing a 3 mL sample M of tin phosphide particles (powder) on a tile plate T, which is an insulating plate. The spark nozzle of a pistol-type gas lighter P is positioned at a distance W = 5 mm from the sample, and the presence or absence of ignition is confirmed by whether or not ignition occurs when a cerium-iron spark S is applied to the tin phosphide particle sample M. The 3 mL of tin phosphide particles (powder) can be weighed, for example, by allowing the tin phosphide particles (powder) to fall naturally into a graduated test tube until it reaches the 3 mL line. In this invention, if ignition is not confirmed even after applying a cerium-iron spark to the tin phosphide 1 to 50 times, it is evaluated as not having ignition properties.

[0032] <Tin Phosphate> The tin phosphate according to the present invention is tin phosphate that does not ignite when the cerium-iron spark ignition test described above is performed, that is, when 3 mL of tin phosphate is placed on an insulating plate and a cerium-iron spark is applied to the tin phosphate 1 to 50 times from a distance of 5 mm from the tin phosphate. By making it such that ignition does not occur even when such a test is performed, it is possible to produce tin phosphate with reduced flammability that is industrially useful.

[0033] The tin phosphide according to the present invention preferably has a tin-to-phosphorus ratio, Sn / P (by weight), of 8.4 to 13.3. By setting the tin phosphide to such an Sn / P (by weight) ratio, the properties of tin phosphide are ensured, while preventing the excessive inclusion of phosphorus-rich tin phosphide with a high proportion of easily ignitable phosphorus and / or phosphorus during the reaction. This results in high-quality tin phosphide with reduced ignition properties.

[0034] The tin phosphide according to the present invention preferably contains substantially no elemental phosphorus (red phosphorus) and / or phosphorus-rich tin phosphide with a high phosphorus ratio during the reaction. Here, "substantially contained" does not mean that the elemental phosphorus content is strictly 0% in all cases. For example, if a trace amount of red phosphorus is unintentionally included, or if a trace amount of red phosphorus is intentionally included but does not affect the ignition properties of the tin phosphide, it is considered to be tin phosphide that contains substantially no elemental phosphorus. An example of unintentional inclusion of a trace amount of red phosphorus is when, in the production facility for tin phosphide, a trace amount of red phosphorus adhering to the container or piping is mixed into the tin phosphide as contamination if a different lot of tin phosphide was previously produced. In such cases, even if a trace amount of red phosphorus is present, it is treated as tin phosphide that contains substantially no elemental phosphorus. The tin phosphide according to the present invention is substantially pure tin phosphide (Sn ４ P ３ It is preferable that the resulting mixture contains almost no unreacted elemental red phosphorus, which was introduced as a raw material. In this case, the molar ratio of tin to phosphorus in the tin phosphide, Sn / P (mol), is the same as that of pure Sn ４ P ３ Since the ratio of tin atoms to phosphorus atoms is 4:3, the ratio can be approximately 1.33.

[0035] The tin phosphide according to the present invention is usually obtained as a powder or granules. The physical properties of the powder or granules are greatly influenced by the particle size and particle size distribution. Therefore, in the tin phosphide according to the present invention, it is necessary to appropriately set the particle size and particle size distribution. In the volume integrated distribution of the particles of the tin phosphide according to the present invention, the 50% particle size (D ５０ It is preferable that the proportion of ) be set to 6-9%. Here, 50% particle size (D ５０ The ratio of ) is the 50% particle diameter (D) relative to the total number of particles calculated from the entire graph in the particle size distribution graph based on volume integration. ５０ It is expressed as the ratio of the number of particles having 50% particle size (D). ５０ The proportion of ) is an indicator that represents the degree of particle size distribution, and the 50% particle size (D ５０When the proportion of ) is large, the particle size distribution becomes sharper, and the 50% particle size (D ５０ When the proportion of ) is small, the particle size distribution becomes broad. In this invention, 50% particle size (D ５０ By setting the proportion of ) to 6-9%, the ignitability of tin phosphide can be further reduced, even in powders that are generally easily ignited.

[0036] Furthermore, the tin phosphide according to the present invention has the following characteristics in the integrated volume distribution of particles: (a) 10% particle diameter (D １０ (b) 1.8 to 11.4 μm, (b) 90% particle size (D ９０ It is preferable that the particle size distribution is set to 21.7 to 386.5 μm. By using tin phosphide having the particle size distribution of (a) and (b) above, the ignition properties of tin phosphide can be further reduced, even if the powder generally has properties that make it easily ignitable. In addition, since the particle size distribution of tin phosphide becomes appropriate, it becomes easier to handle as a powder.

[0037] Furthermore, the tin phosphide according to the present invention has the following characteristics in the integrated volume distribution of particles: (c) 50% particle diameter (D ５０ If the particle size is further 8.5 to 163.7 μm, the flammability of tin phosphide is further reduced, making it even easier to handle as a powder.

[0038] <Method for Producing Tin Phosphate> Next, the method for producing tin phosphate according to the present invention described above will be explained. Figure 2 is a flowchart showing the method for producing tin phosphate according to an embodiment of the present invention, where (a) is a flowchart showing the overall method for producing tin phosphate according to an embodiment of the present invention, (b) is a flowchart showing the details of the reaction process, and (c) is a flowchart showing the details of the washing process. The method for producing tin phosphate according to the present invention is carried out based on the solvothermal method and includes each step shown in Figure 2. The details of each step in the flowchart shown in Figure 2 will be explained below.

[0039] [Input Step] As shown in Figure 2(a), in the method for producing tin phosphide according to the present invention, an input step S1 is performed in which the raw materials are first put into the reaction vessel. The reaction vessel can be any reaction vessel capable of performing the solvothermal method, for example, a pressure vessel in which the inner wall of the reaction vessel is coated with Teflon® and the outer wall is made of stainless steel is used.

[0040] The raw materials introduced in the input step S1 are tin, red phosphorus, and an amine-based solvent. The ratio of tin to red phosphorus, Sn / P (weight), introduced in the input step S1 is preferably set to 5.0 or higher. By setting the Sn / P (weight) of tin to red phosphorus to 5.0 or higher in the input step, excessive amounts of easily ignitable red phosphorus are prevented. As a result, while ensuring the performance of tin phosphide, the tin phosphide does not contain excessive amounts of easily ignitable phosphorus, thus enabling the production of high-quality tin phosphide with reduced ignition properties. Furthermore, if the Sn / P (weight) of tin to red phosphorus introduced in the input step is 5.0 or higher, the Sn / P (weight) of the resulting tin phosphide tends to fall within the preferred range of 8.4 to 13.3 mentioned above.

[0041] Furthermore, ethylenediamine and / or diethylenetriamine are preferably used as the amine solvent introduced in the introduction step S1. For example, by introducing ethylenediamine as the amine solvent along with tin and red phosphorus into the reaction vessel, the red phosphorus is dissolved in ethylenediamine and efficiently contacts the tin, thereby increasing the reactivity between tin and red phosphorus in the reaction steps described later. A similar effect can be expected when red phosphorus is dissolved in diethylenetriamine. Therefore, less unreacted red phosphorus remains in the produced tin phosphide, and high-quality tin phosphide with reduced ignition properties can be produced. In addition, the reaction steps described later, in which tin and red phosphorus react, can be carried out more safely.

[0042] Furthermore, the present invention does not preclude the use of raw materials other than the tin, red phosphorus, and amine-based solvents described above. For the purpose of promoting the reaction or making the reaction safer, other compounds, catalysts, solvents, etc. may be appropriately selected and added to the reaction vessel in step S1, and the following reaction step S2 may be carried out.

[0043] [Reaction Step] Next, in the input step S1, the reaction vessel containing tin, red phosphorus, and an amine-based solvent is sealed, and the reaction step S2 is carried out in which the mixture is heated while being stirred.

[0044] Specifically, reaction step S2 involves, for example, stirring a mixture of tin, red phosphorus, and an amine-based solvent in a reaction vessel while performing the preheating step S2-1, the heating step S2-2, and the high-temperature reaction step S2-3 shown in Figure 2(b). The conditions for preheating step S2-1 are preferably 120 to 170°C for 0.5 to 2 hours, and more preferably 150°C for 1 hour. The conditions for heating step S2-2 are preferably heating to 160 to 200°C over 0.4 to 1 hour, and more preferably 175 to 185°C over 0.5 hours. The conditions for high-temperature reaction step S2-3 are preferably heating at the temperature finally reached in heating step S2-2 for 50 to 110 hours, and more preferably 60 to 80 hours. The temperature and time in each of these steps can be adjusted arbitrarily.

[0045] [Cooling Step] Next, a cooling step S3 is performed on the contents of the reaction vessel, which include tin phosphide, the reaction product after reaction step S2. The cooling step S3 is performed by cooling the reaction vessel to room temperature after reaction step S2 has been carried out.

[0046] [Filtration Process] Next, a filtration process S4 is performed to filter the reaction product that has been cooled in the cooling process S3. In the filtration process S4, tin phosphide, which is a solid component, is filtered out from the reaction product.

[0047] Specifically, the filtration step S4 is carried out by allowing the solid components (tin phosphide) to settle naturally in the reaction vessel, then decanting to remove the supernatant, or by taking the slurry or suspension contents out of the reaction vessel and separating the solid components with a filter.

[0048] [Washing Process] Next, washing process S5 is performed on the solid matter. Specifically, as shown in Figure 2(c), first, water is poured over the solid matter and stirred using a stirring device such as a stainless steel spoon. At this time, ultrasonic waves may be applied to the suspension in which the solid matter is suspended. After that, the solid matter is allowed to settle naturally, and the supernatant liquid is removed by decantation (washing process S5-1). Alternatively, suction filtration may be used. Washing process S5-1 described above may be repeated multiple times as necessary.

[0049] After the water washing step S5-1, ethanol is poured over the solids and stirred using a stirring device. At this time, ultrasonic waves may be applied to the suspension in which the solids are suspended. Then, the solids are allowed to settle naturally, and the supernatant liquid is removed by decantation (ethanol washing step S5-2). The ethanol washing step S5-2 described above may be repeated multiple times as necessary.

[0050] Thus, in the washing process S5, by first performing a water washing process S5-1 in which tin phosphide is washed with water, unreacted red phosphorus and / or a small amount of phosphorus-rich tin phosphide with a high phosphorus ratio remaining during the reaction are removed from the tin phosphide, and the amine-based solvent adhering to the tin phosphide is also removed. The removal of the amine-based solvent can be confirmed by the pH of the surface of the tin phosphide becoming near neutral. Next, by performing an ethanol washing process S5-2 in which tin phosphide is washed with ethanol, any remaining moisture on the tin phosphide is replaced and removed by ethanol, and by drying it, high-quality tin phosphide with reduced ignition properties can be produced.

[0051] [Drying Process] Next, the solids that have been washed in the washing process S5 are subjected to a drying process S6. The drying process S6 may be performed by natural drying or by heating while drying in a dryer. In addition, the drying process S6 is performed in air when performed by natural drying, but it may also be performed under an inert gas or under reduced pressure.

[0052] By carrying out each of the above steps, the series of manufacturing processes is completed. The powder or granules obtained in this way are tin phosphide products obtained by the method for producing tin phosphide according to the present invention.

[0053] The following describes the examples of tin phosphide described above. Each example was carried out according to the steps explained with reference to Figure 2. Details of each example and comparative example are shown in Tables 1 and 2, and the details of each example and comparative example are described below. Table 1 is a table summarizing the reaction conditions in each example, and Table 2 is a table summarizing the properties of the tin phosphide product in each example.

[0054]

[0055]

[0056] <Example 1> [Preparation of tin phosphide] In the input step S1 shown in Figure 2, 7.98 g of tin, 1.59 g of red phosphorus, and 45 mL of ethylenediamine were added to the reaction vessel. The weight ratio of tin to red phosphorus in the added raw materials, Sn / P (weight), was 5.0, and the molar ratio, Sn / P (mol), was 1.31. These raw materials were reacted in the reaction step S2. In the reaction step S2, the mixture was preheated at 150°C for 1 hour as a preheating step S2-1, the temperature was raised to 175°C in 0.5 hours as a heating step S2-2, and the high temperature state was maintained at 175°C for 72 hours as a high-temperature reaction step S2-3. After that, the reaction vessel was cooled to room temperature over 20 hours as a cooling step S3. Then, the slurry contents were removed from the reaction vessel as a filtration step S4, and the solid components were separated using a filter. Furthermore, as a washing step S5, a water washing step S5-1 and an ethanol washing step S5-2 were performed consecutively, and finally, as a drying step S6, the solid components were dried in a groove box for two days. By performing this series of steps, the tin phosphide (powder) of Example 1 was obtained.

[0057] [Composition of Tin Phosphate] The composition of tin phosphate from Example 1 was measured. A X-ray fluorescence (XRF) analyzer (ZSX primus IV, Rigaku Corporation) was used for this measurement. The results of the XRF analysis showed that tin was 89.1% by weight and phosphorus was 10.6% by weight. Therefore, the ratio of tin to phosphorus in the tin phosphate product was 8.4 as Sn / P (by weight).

[0058] [Particle Size Distribution of Tin Phosphate] The particle size and particle size distribution of tin phosphate from Example 1 were measured. A particle size distribution analyzer (Laser Micron Sizer LMS-2000e, manufactured by SEISHIN Corporation) was used for this measurement. As a result of the particle size distribution measurement, the 10% particle size (D) in the volume integrated distribution was １０ ) is 11.4 μm, 50% particle size (D ５０ ) is 163.7 μm, 90% particle size (D ９０ ) was 386.5 μm. Also, D ５０ The percentage was 8.0%.

[0059] [Ignition Properties of Tin Phosphide] The ignition properties of tin phosphide from Example 1 were evaluated. Ignition properties were evaluated using the cerium-iron spark ignition test described above. Specifically, 3 mL of tin phosphide from Example 1 was weighed and placed on an insulating plate (material: ceramic, size: 150 mm x 150 mm x 25 mm). A cerium-iron spark was then applied to the tin phosphide 1 to 50 times using a pistol-type gas lighter from a distance of 5 mm. As a result of the test, ignition was not confirmed in tin phosphide from Example 1 even after being applied to the cerium-iron spark 50 times.

[0060] <Example 2> In the input step S1, 15.99 g of tin, 3.16 g of red phosphorus, and 60 mL of ethylenediamine were added to the reaction vessel. The weight ratio of tin to red phosphorus in the added raw materials, Sn / P (weight), was 5.1, and the molar ratio, Sn / P (mol), was 1.32. These raw materials were reacted in the reaction step S2. In the reaction step S2, the mixture was preheated at 150°C for 1 hour as a preheating step S2-1, the temperature was raised to 185°C in 0.5 hours as a heating step S2-2, and the high temperature state was maintained at 185°C for 72 hours as a high-temperature reaction step S2-3. After that, the cooling step S3, filtration step S4, washing step S5, and drying step S6 were performed in the same manner as in Example 1 to obtain the tin phosphide (powder) of Example 2.

[0061] The composition of the obtained tin phosphide was determined using XRF in the same manner as in Example 1, and it was found to be 90.3% by weight of tin and 9.4% by weight of phosphorus. Therefore, the ratio of tin to phosphorus in the tin phosphide product was 9.6 as Sn / P (by weight).

[0062] When the tin phosphide obtained in Example 2 was measured for particle size and particle size distribution in the same manner as in Example 1, D １０ is 1.8 μm, D ５０ 8.5 μm, D ９０ It was 27.4 μm. Also, D ５０ The percentage was 6.1%.

[0063] Furthermore, when the tin phosphide obtained in Example 2 was subjected to the same cerium-iron spark ignition test as in Example 1, no ignition was observed.

[0064] <Example 3> In the input step S1, 15.99 g of tin, 3.13 g of red phosphorus, and 60 mL of ethylenediamine were added to the reaction vessel. The weight ratio of tin to red phosphorus in the added raw materials, Sn / P (weight), was 5.1, and the molar ratio, Sn / P (mol), was 1.33. These raw materials were reacted in the reaction step S2. The reaction step S2 was carried out under the same conditions as in Example 2, except that the high temperature state was maintained at 185°C for 60 hours as the high-temperature reaction step S2-3. After that, the cooling step S3, filtration step S4, washing step S5, and drying step S6 were carried out in the same manner as in Example 1 to obtain the tin phosphide (powder) of Example 3.

[0065] The composition of the obtained tin phosphide was determined using XRF in the same manner as in Example 1, and it was found to be 91.0% by weight of tin and 8.6% by weight of phosphorus. Therefore, the ratio of tin to phosphorus in the tin phosphide product was 10.6 as Sn / P (by weight).

[0066] When the tin phosphide obtained in Example 3 was measured for particle size and particle size distribution in the same manner as in Example 1, D １０ 4.1 μm, D ５０ 17.3 μm, D ９０ It was 42.8 μm. Also, D ５０ The percentage was 7.7%.

[0067] Furthermore, when the tin phosphide obtained in Example 3 was subjected to the same cerium-iron spark ignition test as in Example 1, no ignition was observed.

[0068] <Example 4> Example 4 is an example to confirm the reproducibility of Example 3. Therefore, the weight ratio of tin to red phosphorus in the raw materials added, Sn / P (weight), was 5.1, and the molar ratio, Sn / P (mol), was 1.33. The adding step S1, reaction step S2, cooling step S3, filtration step S4, washing step S5, and drying step S6 were carried out under the same conditions as in Example 3, thereby obtaining the tin phosphide (powder) of Example 4.

[0069] The composition of the obtained tin phosphide was determined using XRF in the same manner as in Example 1, and it was found to be 90.3% by weight of tin and 9.4% by weight of phosphorus. Therefore, the ratio of tin to phosphorus in the tin phosphide product was 9.6 as Sn / P (by weight).

[0070] When the tin phosphide obtained in Example 4 was measured for particle size and particle size distribution in the same manner as in Example 1, D １０ 2.6 μm, D ５０ 9.5 μm, D ９０ It was 21.7 μm. Also, D ５０ The percentage was 8.2%.

[0071] Furthermore, when the tin phosphide obtained in Example 4 was subjected to a cerium-iron spark ignition test in the same manner as in Example 1, no ignition was observed.

[0072] <Example 5> In the input step S1, 16.04 g of tin, 3.14 g of red phosphorus, and 60 mL of ethylenediamine were added to the reaction vessel. The weight ratio of tin to red phosphorus in the added raw materials, Sn / P (weight), was 5.1, and the molar ratio, Sn / P (mol), was 1.33. These raw materials were reacted in the reaction step S2. The reaction step S2 was carried out under the same conditions as in Example 3. After that, the cooling step S3, filtration step S4, washing step S5, and drying step S6 were carried out in the same manner as in Example 1 to obtain the tin phosphide (powder) of Example 5.

[0073] The composition of the obtained tin phosphide was determined using XRF in the same manner as in Example 1, and it was found to be 92.9% by weight of tin and 7.0% by weight of phosphorus. Therefore, the ratio of tin to phosphorus in the tin phosphide product was 13.3 as Sn / P (by weight).

[0074] When the tin phosphide obtained in Example 5 was measured for particle size and particle size distribution in the same manner as in Example 1, D １０ 9.1 μm, D ５０ 25.7 μm, D ９０ It was 60.5 μm. Also, D ５０ The percentage was 8.2%.

[0075] Furthermore, when the tin phosphide obtained in Example 5 was subjected to a cerium-iron spark ignition test in the same manner as in Example 1, no ignition was observed.

[0076] Next, comparative examples for each of the above-described examples will be explained. In the comparative examples shown below, the weight ratio of tin to red phosphorus in the raw materials added to the reaction vessel, Sn / P (weight) and the molar ratio, Sn / P (mol), mainly in the input step S1, and the conditions of the reaction step S2 differ from those of each example, but the other steps were carried out in the same manner as in each example.

[0077] <Comparative Example 1> In the input step S1, 8.00 g of tin, 1.87 g of red phosphorus, and 60 mL of ethylenediamine were added to the reaction vessel. The weight ratio of tin to red phosphorus in the added raw materials, Sn / P (weight), was 4.3, and the molar ratio, Sn / P (mol), was 1.11. These raw materials were reacted in the reaction step S2. In the reaction step S2, the mixture was preheated at 150°C for 1 hour as a preheating step S2-1, the temperature was raised to 175°C in 0.5 hours as a heating step S2-2, and the high temperature state was maintained at 175°C for 64 hours as a high-temperature reaction step S2-3. After that, the cooling step S3, filtration step S4, washing step S5, and drying step S6 were carried out in the same manner as in Example 1 to obtain tin phosphide (powder) of Comparative Example 1.

[0078] The composition of the obtained tin phosphide was determined using XRF in the same manner as in Example 1, and it was found to be 88.0% by weight of tin and 11.5% by weight of phosphorus. Therefore, the ratio of tin to phosphorus in the tin phosphide product was 7.7 as Sn / P (by weight).

[0079] When the tin phosphide obtained in Comparative Example 1 was measured in the same manner as in Example 1, D １０ 1.7 μm, D ５０ 8.6 μm, D９０ It was 23.2 μm. Also, D ５０ The percentage was 7.0%.

[0080] Furthermore, when the tin phosphide obtained in Comparative Example 1 was subjected to the same cerium-iron spark ignition test as in Example 1, ignition was confirmed after the 23rd application of a spark.

[0081] <Comparative Example 2> In the input step S1, 8.0 g of tin, 1.89 g of red phosphorus, and 60 mL of ethylenediamine were added to the reaction vessel. The weight ratio of tin to red phosphorus in the added raw materials, Sn / P (weight), was 4.2, and the molar ratio, Sn / P (mol), was 1.10. These raw materials were reacted in the reaction step S2. In the reaction step S2, the mixture was preheated at 150°C for 1 hour as a preheating step S2-1, heated to 185°C in 0.5 hours as a heating step S2-2, and maintained at a high temperature of 185°C for 48 hours as a high-temperature reaction step S2-3. After that, the cooling step S3, filtration step S4, washing step S5, and drying step S6 were performed in the same manner as in Example 1 to obtain the tin phosphide (powder) of Comparative Example 2.

[0082] The composition of the obtained tin phosphide was determined using XRF in the same manner as in Example 1, and it was found to be 87.8% by weight of tin and 11.1% by weight of phosphorus. Therefore, the ratio of tin to phosphorus in the tin phosphide product was 7.9 as Sn / P (by weight).

[0083] When the tin phosphide obtained in Comparative Example 2 was measured for particle size and particle size distribution in the same manner as in Example 1, D １０ 2.3 μm, D ５０ 8.4 μm, D ９０ It was 19.6 μm. Also, D ５０ The percentage was 8.0%.

[0084] Furthermore, when the tin phosphide obtained in Comparative Example 2 was subjected to the same cerium-iron spark ignition test as in Example 1, ignition was confirmed on the first spark.

[0085] <Comparative Example 3> In the input step S1, 7.99 g of tin, 1.89 g of red phosphorus, and 60 mL of ethylenediamine were added to the reaction vessel. The weight ratio of tin to red phosphorus in the added raw materials, Sn / P (weight), was 4.2, and the molar ratio, Sn / P (mol), was 1.10. These raw materials were reacted in the reaction step S2. The reaction step S2 was carried out under the same conditions as in Comparative Example 2, except that the high-temperature reaction step S2-3 was performed at a temperature of 185°C for 54 hours. After that, the cooling step S3, filtration step S4, washing step S5, and drying step S6 were performed in the same manner as in Example 1 to obtain the tin phosphide (powder) of Comparative Example 3.

[0086] The composition of the obtained tin phosphide was determined using XRF in the same manner as in Example 1, and it was found to be 88.8% by weight of tin and 10.8% by weight of phosphorus. Therefore, the ratio of tin to phosphorus in the tin phosphide product was 8.2 as Sn / P (by weight).

[0087] When the tin phosphide obtained in Comparative Example 3 was measured for particle size and particle size distribution in the same manner as in Example 1, D １０ 1.6 μm, D ５０ 6.6 μm, D ９０ It was 15.9 μm. Also, D ５０ The percentage was 7.7%.

[0088] Furthermore, when the tin phosphide obtained in Comparative Example 3 was subjected to the same cerium-iron spark ignition test as in Example 1, ignition was confirmed on the first spark.

[0089] <Discussion> Based on the examples and comparative examples shown in Tables 1 and 2, the following findings were obtained regarding the ignition properties of tin phosphide according to the present invention.

[0090] The Sn / P (weight) ratio in the raw materials used differed between Examples 1-5 and Comparative Examples 1-3. Specifically, in Examples 1-5, the Sn / P (weight) ratio in the raw materials used was 5.0 or higher, while in Comparative Examples 1-3, it was less than 5.0. This indicates that, in the method for producing tin phosphide according to the present invention, by setting the Sn / P (weight) ratio in the raw materials used to 5.0 or higher, it is possible to produce tin phosphide with reduced ignition properties.

[0091] Furthermore, as shown in Examples 1 to 5, by having a Sn / P (weight) ratio of 8.4 to 13.3 in the tin phosphide product, it is possible to obtain tin phosphide with reduced ignition properties.

[0092] Furthermore, as shown in Examples 1 to 5, when the molar ratio of tin to red phosphorus, Sn / P (mol), is set to 1.33 or a value close to the stoichiometric ratio, the red phosphorus reacts almost completely with the tin, producing pure tin phosphide and / or tin-rich tin phosphide. Such tin phosphide is less flammable because it substantially does not contain easily combustible elemental phosphorus and / or phosphorus-rich tin phosphide with a high proportion of phosphorus during the reaction. On the other hand, in Comparative Examples 1 to 3, the molar ratio of tin to red phosphorus, Sn / P (mol), is 1.1, and a large amount of unreacted elemental phosphorus remains, making it easily ignitable.

[0093] The present invention provides a method for producing tin phosphide, and the tin phosphide produced thereby can be used in various industrial fields, such as the electronics industry.

Claims

1. Tin phosphide, wherein 3 mL of the tin phosphide is placed on an insulating plate, and a cerium-iron spark is applied to the tin phosphide 1 to 50 times from a position 5 mm away from the tin phosphide, and no ignition is observed.

2. The tin phosphide according to claim 1, wherein the ratio of tin to phosphorus, Sn / P (by weight), is 8.4 to 13.

3.

3. The tin phosphide according to claim 2, which substantially does not contain elemental phosphorus and / or phosphorus-rich tin phosphide.

4. In the integrated volume distribution of particles, the 50% particle diameter (D ５０ The tin phosphide according to any one of claims 1 to 3, wherein the proportion of ) is 6 to 9%.

5. In the integrated volume distribution of particles, (a) 10% particle diameter (D １０ (b) 1.8 to 11.4 μm, (b) 90% particle size (D ９０ The tin phosphide according to any one of claims 1 to 3, wherein the ) is 21.7 to 386.5 μm.

6. A method for producing tin phosphide, comprising: an input step of adding tin, red phosphorus, and an amine-based solvent to a reaction vessel; a reaction step of sealing the reaction vessel and heating it while stirring; a cooling step of cooling the reaction vessel; a filtration step of removing the contents from the reaction vessel and filtering out the tin phosphide; a washing step of washing the filtered tin phosphide; and a drying step of drying the washed tin phosphide.

7. The method for producing tin phosphide according to claim 6, wherein in the input step, the ratio of tin to red phosphorus, Sn / P (by weight), is set to 5.0 or more.

8. The method for producing tin phosphide according to claim 6 or 7, wherein the amine solvent is ethylenediamine and / or diethylenetriamine.

9. The method for producing tin phosphide according to claim 6 or 7, wherein in the washing step, the tin phosphide is washed with water and then washed with ethanol.

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