Tin phosphide, and method for producing tin phosphide

Abstract

To provide tin phosphide with reduced ignition properties. [Solution] The tin phosphide is such that when 3 mL of 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 distance of 5 mm, no ignition is observed, the ratio of tin to phosphorus (Sn / P by weight) is 8.4 to 13.3, and it substantially does not contain elemental phosphorus and / or phosphorus-rich tin phosphide.

Description

[Technical Field]

[0001] This invention relates to tin phosphide and a method for producing tin phosphide. [Background technology]

[0002] Tin phosphide, a compound of tin (Sn) and phosphorus (P), has recently attracted attention for its potential applications. Tin phosphide is known in several forms, including tetrastannous triphosphide (Sn4P3), tristannous diphosphide (Sn3P2), tristannous tetraphosphide (Sn3P4), and monostannous triphosphide (SnP3). Of these, tetrastannous triphosphide (Sn4P3) is an industrially promising material, and various applications are being explored. The present invention's "Tin Phosphide and Method for Producing Tin Phosphide" also focuses on tetrastannous triphosphide (Sn4P3), and hereafter, tetrastannous triphosphide (Sn4P3) will be referred to simply as "tin phosphide."

[0003] Although at the laboratory level, various methods have been attempted to produce tin phosphide. For example, Patent Document 1 describes a method for producing tin phosphide (deposition method) in which pulverized phosphorus and tin powders are mixed, pressed into a film, and then a pulsed laser is applied to deposit tin phosphide onto it.

[0004] Furthermore, 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, cooled, and the cooled reaction product is washed and dried to obtain tin phosphide. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Chinese Patent Application Publication No. 101289176 Specification [Patent Document 2] Chinese Patent Application Publication No. 112978693 Specification [Overview of the project] [Problems that the invention aims to solve]

[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 property that is less likely to ignite and is safer.

[0007] Tin phosphide is generally produced using metallic tin and red phosphorus as raw materials. Among these, although red phosphorus does not have the intense reactivity of yellow phosphorus as a simple substance of phosphorus, it is still designated as a Class 2 dangerous substance under the Fire Service Act in Japan and is a substance that is prone to ignition by a flame, so great care is required in handling. Even in the case of tin phosphide, there are sometimes cases where ignition occurs due to the residual red phosphorus as a raw material. Regarding the risk of ignition of such tin phosphide, although it has been potentially recognized, since industrial production has hardly been carried out, no countermeasures have been taken in conventional tin phosphide including the above-mentioned Patent Document 1 and Patent Document 2, and this is the current situation.

[0008] The present invention has been made in view of the above problems, and an object thereof is to provide tin phosphide with reduced flammability. Furthermore, an object is to provide a method for producing tin phosphide that enables such tin phosphide with reduced flammability to be industrially produced.

Means for Solving the Problems

[0009] The characteristic configuration of the tin phosphide according to the present invention for solving the above problems is tin phosphide, When placing 3 mL of the tin phosphide on a heat-insulating plate and applying a cerium-iron spark to the tin phosphide 1 to 50 times from a position 5 mm away from the tin phosphide, ignition is not confirmed.

[0010] The method of "placing 3 mL of tin phosphide on a heat-insulating plate, applying a cerium-iron spark to the tin phosphide from a position 5 mm away from the tin phosphide, and determining the flammability" employed in the present invention is a test method conforming to the cerium-iron spark test, which is an index of flammability defined by the Federal Institute for Materials Research and Testing (BAM) in Germany. According to the tin phosphide of this configuration, even when a cerium-iron spark is applied to the tin phosphide 1 to 50 times by a method conforming to the flammability test defined by the German Federal Institute for Materials Research and Testing (BAM), a property in which ignition is not confirmed can be achieved, and thus, tin phosphide with industrially useful reduced flammability can be obtained.

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

[0012] According to the tin phosphide of this configuration, by setting Sn / P (weight) to 8.4 to 13.3, while ensuring the properties of tin phosphide, phosphorus that is prone to ignition is not excessively contained in the tin phosphide, so that high-quality tin phosphide with reduced flammability can be obtained.

[0013] In the tin phosphide according to the present invention, it is preferable that elemental phosphorus and / or phosphorus-rich tin phosphide are not substantially contained.

[0014] According to the tin phosphide of this configuration, since elemental phosphorus that is prone to combustion and / or phosphorus-rich tin phosphide with a high phosphorus ratio during the reaction is not substantially contained, tin phosphide with further reduced flammability can be obtained. <00​​​​​​​​​​​​​​​​​​​​​​ (b) 90% particle size (D 90 ) is 21.7~386.5μm It is preferable that this be the case.

[0018] With this tin phosphide configuration, by using tin phosphide having the particle size distributions described in (a) and (b) above, the ignitability of tin phosphide can be further reduced, even if the powder generally has properties that make it easily ignitable. In addition, because the particle size distribution of tin phosphide becomes appropriate, it becomes easier to handle as a powder.

[0019] Furthermore, the characteristic configuration of the method for producing tin phosphide according to the present invention, which solves the above problems, is: The process involves adding tin, red phosphorus, and an amine-based solvent to a reaction vessel, The reaction step involves sealing the reaction vessel and heating it while stirring, A cooling step for cooling the reaction vessel, A filtration step is performed to remove the contents from the reaction vessel and filter out the tin phosphide, A washing process to wash the filtered tin phosphide, A drying process to dry the washed tin phosphide and It is preferable to include it.

[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, In the aforementioned input step, it is preferable that the ratio of tin to red phosphorus, Sn / P (by weight), is set to 5.0 or higher.

[0022] According to the tin phosphide manufacturing method of this configuration, by setting the Sn / P (weight) ratio of the tin to red phosphorus introduced in the input process to 5.0 or higher, the performance of the 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, In the aforementioned cleaning process, it is preferable to wash the tin phosphide with water and then 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 surface of the tin phosphide 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. [Brief explanation of the drawing]

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

Embodiments for Carrying out the Invention

[0028] Tin phosphide (tin trisphosphide (Sn4P3)) according to the present invention and a method for manufacturing tin phosphide will be described. However, the present invention is not limited to the configurations described in the embodiments and examples described below.

[0029] <BAM Ignition Test> The tin phosphide according to the present invention is tin phosphide having a property with reduced flammability. Here, the evaluation of the flammability of a substance is often carried out by a test method defined 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 an actual industry standard. Therefore, first, the outline of the BAM ignition test will be described.

[0030] The BAM ignition test includes a small gas flame test, a red-hot iron rod test, a fuse test, and a cerium - iron spark ignition test. Among these, the cerium - iron spark ignition test is a test method for examining whether a substance is likely to ignite in response to an external spark, and is suitable for confirming the flammability of a compound using a substance that is originally likely to ignite (red phosphorus in the present invention) as a raw material.

[0031] Figure 1 is a schematic diagram illustrating the outline 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, samples that did not ignite after being struck with a cerium-iron spark 1 to 50 times were evaluated as lacking ignition properties.

[0032] <Tin phosphide> The tin phosphide according to the present invention is tin phosphide that does not ignite when subjected to the cerium-iron spark ignition test described above, that is, when 3 mL of 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 distance of 5 mm from the tin phosphide. By making the tin phosphide such that no ignition is observed even when subjected to such a test, it is possible to produce tin phosphide 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 ratio (by weight), 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 does not substantially contain elemental phosphorus (red phosphorus) and / or phosphorus-rich tin phosphide with a high phosphorus ratio during the reaction. Here, "not substantially contained" does not mean that the content of elemental phosphorus is strictly 0% in any case. For example, when an extremely small amount of red phosphorus is inadvertently contained, or when an extremely small amount of red phosphorus is intentionally contained but does not affect the ignition property of tin phosphide, it is regarded as tin phosphide that does not substantially contain elemental phosphorus. Examples of the case where an extremely small amount of red phosphorus is inadvertently contained include cases where, in the production equipment of tin phosphide, when tin phosphide of a previous batch was produced, an extremely small amount of red phosphorus adhering to the container or piping was mixed into the tin phosphide as contamination. In such cases, even if it contains a very small amount of red phosphorus, it is treated as tin phosphide that does not substantially contain elemental phosphorus. The tin phosphide according to the present invention is preferably formed substantially by pure tin phosphide (Sn4P3), and substantially no unreacted elemental red phosphorus remains as a raw material. In this case, the molar ratio of tin to phosphorus in tin phosphide, Sn / P (mol), can be about 1.33 because the number of tin atoms: the number of phosphorus atoms in pure Sn4P3 is 4:3.

[0035] The tin phosphide according to the present invention is usually obtained as a powder or granular material. The physical properties of the powder or granular material are greatly affected by the particle size and particle size distribution. Therefore, it is also necessary to appropriately set the particle size and particle size distribution in the tin phosphide according to the present invention. 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 set to 6 to 9%. Here, the ratio of the 50% particle size (D 50 ) is represented as the ratio of the number of particles having the 50% particle size (D 50 ) to the total number of particles calculated from the entire graph in the graph of the particle size distribution by volume integral distribution. The ratio of the 50% particle size (D 50 ) is an index representing the degree of the particle size distribution. A larger ratio of the 50% particle size (D 50 ) results in a sharper particle size distribution, and a larger ratio of the 50% particle size (D 50When 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, in terms of the integrated volume distribution of particles, (a) 10% particle size (D 10 ) is 1.8~11.4μm, (b) 90% particle size (D 90 ) is 21.7~386.5μm It is preferable to set it to (a) and (b) above. By using tin phosphide having the particle size distribution described in (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, in the integrated volume distribution of particles, the tin phosphide according to the present invention (c) 50% particle size (D 50 ) is 8.5~163.7μm If these conditions are also met, the flammability of tin phosphide is further reduced, making it even easier to handle as a powder.

[0038] <Method for producing tin phosphide> Next, the method for producing tin phosphide according to the present invention described above will be explained. Figure 2 is a flowchart showing the 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 step, and (c) is a flowchart showing the details of the washing step. The method for producing tin phosphide 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] [Feeding process] As shown in Figure 2(a), in the method for producing tin phosphide according to the present invention, first, an input step S1 is performed in which the raw materials are put into a 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 resulting 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 process] Next, in the input step S1, the reaction vessel containing tin, red phosphorus, and an amine-based solvent is sealed, and the mixture is heated while being stirred in the reaction step S2.

[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 carrying out 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 120-170°C for 0.5-2 hours, and more preferably 150°C for 1 hour. The conditions for heating step S2-2 are preferably heating to 160-200°C over 0.4-1 hours, and more preferably to 175-185°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 50-110 hours, and more preferably 60-80 hours. The temperature and time in each of these steps can be adjusted as needed.

[0045] [Cooling process] 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. Cooling step S3 is performed by cooling the reaction vessel to room temperature after reaction step S2 has been completed.

[0046] [Filtration process] Next, a filtration step S4 is performed to filter out the reaction product that has been cooled in the cooling step S3. In the filtration step 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, a washing step S5 is performed on the solids. Specifically, as shown in Figure 2(c), water is first poured over the solids and stirred using a stirring device such as a stainless steel spoon. At this time, ultrasonic waves may be applied to the suspension of suspended solids. After that, the solids are allowed to settle naturally, and the supernatant liquid is removed by decantation (water washing step S5-1). Alternatively, suction filtration may be used. The water washing step 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, a drying step S6 is performed on the solids that have undergone the washing step S5. The drying step S6 may be performed by natural drying or by heating while drying in a dryer. In addition, while the drying step S6 is performed in air when performed by natural drying, 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. [Examples]

[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] [Table 1]

[0055] [Table 2]

[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, the washing process S5 consisted of a water washing process S5-1 followed by an ethanol washing process S5-2, and finally, the solid components were dried in a groove box for two days as a drying process S6. By performing these series of steps, the tin phosphide (powder) of Example 1 was obtained.

[0057] [Composition of tin phosphide] The composition of tin phosphide from Example 1 was measured. A XRF (X-ray fluorescence) analyzer (ZSX primus IV, Rigaku) ​​was used for this measurement. XRF analysis revealed that the tin content was 89.1% by weight and the phosphorus content was 10.6% by weight. Therefore, the ratio of tin to phosphorus in the resulting tin phosphide was 8.4 (Sn / P by weight).

[0058] [Particle size distribution of tin phosphide] The particle size and particle size distribution of tin phosphide in 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. The ignition properties were evaluated using the cerium-iron spark ignition test described above. Specifically, 3 mL of tin phosphide from Example 1 was weighed out and placed on an insulating plate (material: ceramic, size: 150 mm x 150 mm x 25 mm). Then, a cerium-iron spark was struck onto the tin phosphide 1 to 50 times using a pistol-type gas lighter from a distance of 5 mm from the tin phosphide. The test results showed that tin phosphide from Example 1 did not ignite even after being exposed to a 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(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 reaction step S2-3 was performed at a temperature of 185°C for 60 hours. Subsequently, 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 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(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 is 4.1 μm, D 50 It is 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 a cerium-iron spark ignition test in the same manner 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(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 is 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 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 step S2. Step S2 was carried out under the same conditions as in Example 3. Subsequently, the cooling step S3, filtration step S4, washing step S5, and drying step S6 were performed 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(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 is 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, then heated to 175°C in 0.5 hours as a temperature increase step S2-2, and finally maintained at a high temperature of 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 performed 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(weight).

[0079] When the tin phosphide obtained in Comparative Example 1 was measured for particle size and particle size distribution in the same manner as in Example 1, D 10 is 1.7 μm, D 50 is 8.6 μm, D 90 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, then heated to 185°C in 0.5 hours as a temperature increase step S2-2, and finally 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 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(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 is 2.3 μm, D50 is 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. Subsequently, 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 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(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 is 1.6 μm, D 50 is 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] <Consideration> 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 1-5, 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 contains virtually no 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 1-3, 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 highly flammable. [Industrial applicability]

[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. It is tin phosphide, The aforementioned tin phosphide is tetratin triphosphide. Tin phosphide in which ignition is not observed 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.

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 size (D １０ ) is 1.8 to 11.4 μm, (b) 90% particle size (D ９０ ) 21.7–386.5 μm The tin phosphide according to any one of claims 1 to 3.

6. The process involves adding tin, red phosphorus, and an amine-based solvent to a reaction vessel, The reaction step involves sealing the reaction vessel and heating it while stirring, A cooling step for cooling the reaction vessel, A filtration step is performed to remove the contents from the reaction vessel and filter out the tin phosphide, A washing process to wash the filtered tin phosphide, A drying process to dry the washed tin phosphide and A method for producing tin phosphide as tetrastannous triphosphate, encompassing all other aspects.

7. The method for producing tin phosphide according to claim 6, wherein in the aforementioned 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-based 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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